Herbicides

ABSTRACT

Bicyclic dione compounds, and derivatives thereof, which are suitable for use as herbicides. formula (I)

This application is a 371 of International Application No.PCT/EP2008/006279 filed Jul. 30, 2008, which claims priority to GB0714981.8 filed Aug. 1, 2007, the contents of which are incorporatedherein by reference.

The present invention relates to novel, herbicidally active cyclicdiones, and derivatives thereof, to processes for their preparation, tocompositions comprising those compounds, and to their use in controllingweeds, especially in crops of useful plants, or in inhibiting plantgrowth.

Cyclic diones having herbicidal action are described, for example, inU.S. Pat. Nos. 4,175,135 and 4,209,532.

Novel bicyclic diones, and derivatives thereof, having herbicidal andgrowth-inhibiting properties have now been found.

The present invention accordingly relates to compounds of formula I

wherein

-   R¹ and R² are independently of each other hydrogen, C₁-C₆alkyl,    C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,    C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆haloalkenyloxy, C₃-C₆alkynyloxy,    C₁-C₄alkoxyC₁-C₄alkyl, C₁-C₄alkoxyC₁-C₄alkoxy,    C₁-C₄alkoxyC₁-C₄alkoxyC₁-C₄alkyl, C₁-C₆alkylthio,    C₁-C₄alkylthioC₁-C₄alkyl, C₁-C₄alkylsulfinyl,    C₁-C₄alkylsulfinylC₁-C₄alkyl, C₁-C₄alkylsulfonyl,    C₁-C₄alkylsulfonylC₁-C₄alkyl, hydroxy-C₁-C₄alkyl,    C₁-C₆haloalkoxyC₁-C₄alkyl, C₃-C₆alkenyloxyC₁-C₄alkyl,    C₃-C₆haloalkenyloxyC₁-C₄alkyl, C₃-C₆alkynyloxyC₁-C₄alkyl,    C₁-C₆cyanoalkyl, C₁-C₆cyanoalkoxy, C₁-C₄cyanoalkoxyC₁-C₄alkyl,    hydroxy, C₁-C₆alkylcarbonyl, carboxy, C₁-C₆alkoxycarbonyl,    C₁-C₆alkylaminocarbonyl, di-C₁-C₆alkylaminocarbonyl,    tri(C₁-C₄alkyl)silyl or tri(C₁-C₄alkyl)silyloxy,-   D is optionally substituted C₁-C₃alkylene,-   E is optionally substituted C₁-C₃alkylene or optionally substituted    C₂-C₃alkenylene,-   Het is a an optionally substituted monocyclic or bicyclic    heteroaromatic ring; and-   G is hydrogen, an alkali metal, alkaline earth metal, sulfonium,    ammonium or a latentiating group.

In the substituent definitions of the compounds of the formula I, thealkyl radicals and alkyl moieties of alkoxy, alkylsulfonyl etc. having 1to 6 carbon atoms are preferably methyl, ethyl as well as propyl, butyl,pentyl and hexyl, in form of their straight and branched isomers.

The alkenyl and alkynyl radicals having 2 to 6 carbon atoms can bestraight or branched and can contain more than 1 double or triple bond.Examples are vinyl, allyl, propargyl, butenyl, butynyl, pentenyl andpentynyl.

Preferred halogens are fluorine, chlorine and bromine.

Substituted C₁-C₃alkylene and substituted C₂-C₃alkenylene unitsrepresent saturated and unsaturated carbon chains which may besubstituted once or more than once by substituents such as C₁-C₆alkyl,C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₃-C₇cycloalkyl, C₃-C₇cycloalkylC₁-C₄alkyl, C₅-C₇cycloalkenyl,C₅-C₇cycloalkenylC₁-C₄alkyl, phenylC₁-C₄alkyl, substitutedphenylC₁-C₄alkyl, heteroarylC₁-C₄alkyl and substitutedheteroarylC₁-C₄alkyl, heterocyclylC₁-C₄alkyl and substitutedheterocyclylC₁-C₄alkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₄alkoxyC₁-C₄alkyl, C₁-C₄alkoxyC₁-C₄alkoxy,C₁-C₄alkoxyC₁-C₄alkoxyC₁-C₄alkyl, C₁-C₆alkylthio,C₁-C₄alkylthioC₁-C₄alkyl, C₁-C₄alkylsulfinylC₁-C₄alkyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylsulfonylC₁-C₄alkyl, halo, cyano, nitro,C₁-C₆cyanoalkyl, C₁-C₆cyanoalkoxy, hydroxy, C₃-C₆alkenyloxy,C₃-C₆haloalkenyloxy, C₃-C₆alkynyloxy, phenoxy, substituted phenoxy,heteroaryloxy, substituted heteroaryloxy, heterocyclyloxy, substitutedheterocyclyloxy, phenylC₁-C₄alkoxy, substituted phenylC₁-C₄alkoxy,heteroarylC₁-C₄alkoxy, substituted heteroarylC₁-C₄alkoxy,heterocyclylC₁-C₄alkoxy, substituted heterocyclylC₁-C₄alkoxy,hydroxy-C₁-C₄alkyl, C₁-C₆haloalkoxyC₁-C₄alkyl,C₃-C₆alkenyloxyC₁-C₄alkyl, C₃-C₆haloalkenyloxyC₁-C₄alkyl,C₃-C₆alkynyloxyC₁-C₄alkyl, C₁-C₄alkylcarbonyloxyC₁-C₄alkyl,C₁-C₄alkoxycarbonylC₁-C₄alkyl, C₁-C₄alkylaminocarbonyloxyC₁-C₄alkyl,di-C₁-C₄alkylaminocarbonyloxyC₁-C₄alkyl, phenoxyC₁-C₄alkyl, substitutedphenoxyC₁-C₄alkyl, heteroaryloxyC₁-C₄alkyl, substitutedheteroaryloxyC₁-C₄alkyl, heterocyclyloxyC₁-C₄alkyl, substitutedheterocyclyloxyC₁-C₄alkyl, phenylC₁-C₄alkoxyC₁-C₄alkyl, substitutedphenylC₁-C₄alkoxyC₁-C₄alkyl, heteroarylC₁-C₄alkoxyC₁-C₄alkyl,substituted heteroarylC₁-C₄alkoxyC₁-C₄alkyl,heterocyclylC₁-C₄alkoxyC₁-C₄alkyl, substitutedheterocyclylC₁-C₄alkoxyC₁-C₄alkyl, C₁-C₆cyanoalkoxyC₁-C₄alkyl,tri(C₁-C₄alkyl)silyloxyC₁-C₄alkyl, carboxy, C₁-C₄alkylcarbonyl,C₁-C₄alkoxycarbonyl, amidocarbonyl, C₁-C₄alkylaminocarbonyl,di-C₁-C₄alkylaminocarbonyl, phenylaminocarbonyl, substitutedphenylaminocarbonyl, heteroarylaminocarbonyl, substitutedheteroarylcarbonyl, C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxycarbonyloxy,C₁-C₆alkylaminocarbonyloxy, diC₁-C₄alkylaminocarbonyloxy,C₁-C₆alkylaminothiocarbonyloxy, phenylcarbonyloxy, substitutedphenylcarbonyloxy, heteroarylcarbonyloxy, substitutedheteroarylcarbonyloxy, heterocyclylcarbonyloxy, substitutedheterocyclylcarbonyloxy, amino, C₁-C₄alkylcarbonylamino,C₁-C₄alkoxycarbonylamino, (C₁-C₄alkylthio)carbonylamino,C₁-C₄alkoxythiocarbonylamino, C₁-C₄alkyl(thiocarbonyl)amino,C₁-C₄alkylaminocarbonylamino, di-C₁-C₄alkylaminocarbonylamino,phenylcarbonylamino, substituted phenylcarbonylamino,heteroarylcarbonylamino, substituted heteroarylcarbonylamino,phenoxycarbonylamino, substituted phenoxycarbonylamino,phenylaminocarbonylamino, substituted phenylaminocarbonylamino,C₁-C₄alkylsulfonylamino, C₁-C₄haloalkylsulfonylamino,phenylsulfonylamino, substituted phenylsulfonylamino,C₁-C₄alkylcarbonylaminoC₁-C₄alkyl, C₁-C₄alkoxycarbonylaminoC₁-C₄alkyl,(C₁-C₄alkylthio)carbonylaminoC₁-C₄alkyl,C₁-C₄alkoxythiocarbonylaminoC₁-C₄alkyl,C₁-C₄alkyl(thiocarbonyl)aminoC₁-C₄alkyl,C₁-C₄alkylaminocarbonylaminoC₁-C₄alkyl,di-C₁-C₄alkylaminocarbonylaminoC₁-C₄alkyl,phenylcarbonylaminoC₁-C₄alkyl, substitutedphenylcarbonylaminoC₁-C₄alkyl, heteroarylcarbonylaminoC₁-C₄alkyl,substituted heteroarylcarbonylaminoC₁-C₄alkyl,phenoxycarbonylaminoC₁-C₄alkyl, substitutedphenoxycarbonylaminoC₁-C₄alkyl, phenylaminocarbonylaminoC₁-C₄alkyl,substituted phenylaminocarbonylaminoC₁-C₄alkyl,C₁-C₄alkylsulfonylaminoC₁-C₄alkyl,C₁-C₄haloalkylsulfonylaminoC₁-C₄alkyl, phenylsulfonylaminoC₁-C₄alkyl,substituted phenylsulfonylaminoC₁-C₄alkyl, tri(C₁-C₄alkyl)silyloxy,phenyl and substituted phenyl, heteroaryl and substituted heteroaryl,heterocyclyl and substituted heterocyclyl. Preferably, the C₁-C₃alkyleneand C₂-C₃alkenylene groups D and E are unsubstituted, or are substitutedonce or twice by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkoxyC₁-C₄alkyl, halogenor hydroxy.

Where two preferably adjacent substituents are present on theC₁-C₃alkylene and C₂-C₃alkenylene groups these substituents mayadditionally join together to form a 3-7 membered saturated ring, whichmay optionally contain one or more heteroatoms selected from oxygen,sulfur or nitrogen, or may form a 5-7 membered unsaturated ring, whichmay optionally contain one or more heteroatoms which are selected fromoxygen, sulfur or nitrogen. Preferred rings which are formed aredioxolane rings, optionally substituted once or twice by C₁-C₃alkyl.Suitable examples of heteroaromatic rings are, for example, thienyl,furyl, pyrrolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl,pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl,pyrazinyl, pyridazinyl, triazinyl, oxadiazolyl and thiadiazolyl, and,where appropriate, N-oxides and salts thereof.

These heteroaromatic rings can be substituted by one or moresubstituents, where preferred substituents may be selected fromC₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₁-C₄haloalkyl, C₃-C₇cycloalkyl,C₃-C₇halocycloalkyl, C₅-C₇cycloalkenyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy,C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,C₁-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfonyl,fluoro, chloro, bromo, iodo, cyano, nitro, hydroxy-C₁-C₄alkyl, formyl,carboxy, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, amidocarbonyl,C₁-C₄alkylaminocarbonyl, di-C₁-C₄alkylaminocarbonyl, amino,C₁-C₄alkylcarbonylamino, C₁-C₄alkoxycarbonylamino,C₁-C₄alkylaminocarbonylamino, diC₁-C₄alkylaminocarbonylamino,C₁-C₄alkylsulfonylamino, C_(r) C₄haloalkylsulfonylamino,C₁-C₄alkylsulfonyloxy and C₁-C₄haloalkylsulfonyloxy and are preferablyselected from C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, halo, cyano andnitro, especially C₁-C₂alkyl, C₁-C₂alkoxy, C₁-C₂haloalkoxy, fluoro,chloro and cyano.

The group G denotes hydrogen, an alkali metal cation such as sodium orpotassium, alkaline earth metal cation such as calcium, sulfonium cation(preferably —S(C₁-C₆alkyl₃)⁺) or ammonium cation (preferably —NH₄ ⁺ or—N(C₁-C₆alkyl)₄ ⁺), or C₁-C₆alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl or alatentiating group. The latentiating group G is preferably selected fromC₁-C₈ alkyl, C₂-C₈ haloalkyl, phenylC₁-C₈alkyl (wherein the phenyl mayoptionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, halogen, cyano or by nitro), heteroarylC₁-C₈alkyl(wherein the heteroaryl may optionally be substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio,C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro),C₃-C₈ alkenyl, C₃-C₈ haloalkenyl, C₃-C₈ alkynyl, C(X^(a))—R^(a),C(X^(b))—X^(c)—R^(b), C(X^(d))—N(R^(c))—R^(d), —SO₂—R^(e),—P(X^(e))(R^(f))—R^(g) or CH₂—X^(f)—R^(h) wherein X^(a), X^(b), X^(c),X^(d), X^(e) and X^(f) are independently of each other oxygen or sulfur;

-   R^(a) is H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl,    C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl,    C₁-C₁₀aminoalkyl, C₁-C₅alkylaminoC₁-C₅alkyl,    C₂-C₈dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl,    C₁-C₅alkoxyC₁-C₅alkyl, C₃-C₅alkenyloxyC₁-C₅alkyl,    C₃-C₅alkynyloxyC₁-C₅alkyl, C₁-C₅alkylthioC₁-C₅alkyl,    C₁-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl,    C₂-C₈alkylideneaminoxyC₁-C₅alkyl, C₁-C₅alkylcarbonylC₁-C₅alkyl,    C₁-C₅alkoxycarbonylC₁-C₅alkyl, aminocarbonylC₁-C₅alkyl,    C₁-C₅alkylaminocarbonylC₁-C₅alkyl,    C₂-C₈dialkylaminocarbonylC₁-C₅alkyl,    C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,    N—C₁-C₅alkylcarbonyl-N—C₁-C₅alkylaminoC₁-C₅alkyl,    C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl    may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro),    heteroarylC₁-C₅alkyl, (wherein the heteroaryl may optionally be    substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,    C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₂-C₅haloalkenyl,    C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or    nitro, heteroaryl or heteroaryl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or    nitro,-   R^(b) is C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₂-C₁₀haloalkyl,    C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₂-C₁₀aminoalkyl,    C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl,    C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl,    C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl,    C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl,    C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxyC₁-C₅alkyl,    C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl,    aminocarbonylC₁-C₅alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl,    C₂-C₈dialkylaminocarbonylC₁-C₅alkyl,    C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,    N—C₁-C₅alkylcarbonyl-N—C₁-C₅alkylaminoC₁-C₅alkyl,    C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl    may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro),    heteroarylC₁-C₅alkyl, (wherein the heteroaryl may optionally be    substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,    C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₃-C₅haloalkenyl,    C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or    nitro, heteroaryl or heteroaryl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or    nitro,-   R^(c) and R^(d) are each independently of each other hydrogen,    C₁-C₁₀alkyl, C₃-C₁₀alkenyl, C₃-C₁₀alkynyl, C₂-C₁₀haloalkyl,    C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl,    C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl,    C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl,    C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl,    C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl,    C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxyC₁-C₅alkyl,    C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl,    aminocarbonylC₁-C₅alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl,    C₂-C₈dialkylaminocarbonylC₁-C₅alkyl,    C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,    N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl,    C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl    may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro),    heteroarylC₁-C₅alkyl, (wherein the heteroaryl may optionally be    substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,    C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₂-C₅haloalkenyl,    C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or    nitro, heteroaryl or heteroaryl substituted by C₁-C₃ alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or    nitro, heteroarylamino or heteroarylamino substituted by C₁-C₃    alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano    or nitro, diheteroarylamino or diheteroarylamino substituted by    C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,    cyano or nitro, phenylamino or phenylamino substituted by    C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,    cyano or by nitro, diphenylamino or diphenylamino substituted by    C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,    cyano or by nitro, amino, C₁-C₃alkylamino, C₁-C₃dialkylamino,    C₁-C₃alkoxy or C₃-C₇cycloalkylamino, di-C₃-C₇cycloalkylamino or    C₃-C₇cycloalkoxy or R^(c) and R^(d) may join together to form a 3-7    membered ring, optionally containing one heteroatom selected from O    or S and optionally substituted by 1 or 2 C₁-C₃alkyl groups,-   R^(e) is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,    C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl,    C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₅dialkylaminoC₁-C₅alkyl,    C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl,    C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl,    C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl,    C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxyC₁-C₅alkyl,    C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl,    aminocarbonylC₁-C₅alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl,    C₂-C₅dialkylaminocarbonylC₁-C₅alkyl,    C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,    N—C₁-C₅alkylcarbonyl-N—C₁-C₅alkylaminoC₁-C₅alkyl,    C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl    may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro),    heteroarylC₁-C₅alkyl (wherein the heteroaryl may optionally be    substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,    C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₂-C₅haloalkenyl,    C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or    nitro, heteroaryl or heteroaryl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, amino    or by nitro, heteroarylamino or heteroarylamino substituted by    C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,    cyano or by nitro, diheteroarylamino or diheteroarylamino    substituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,    C₁-C₃haloalkoxy, halogen, cyano or nitro, phenylamino or phenylamino    substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,    C₁-C₃haloalkoxy, halogen, cyano, nitro, amino, diphenylamino, or    diphenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro, or    C₃-C₇cycloalkylamino, diC₃-C₇cycloalkylamino or C₃-C₇cycloalkoxy,    C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy, C₁-C₅alkylamino or    C₂-C₅dialkylamino,-   R^(f) and R^(g) are each independently of each other C₁-C₁₀alkyl,    C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀alkoxy, C₁-C₁₀haloalkyl,    C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl,    C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₅dialkylaminoC₁-C₅alkyl,    C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl,    C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl,    C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl,    C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₅alkylideneaminoxyC₁-C₅alkyl,    C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl,    aminocarbonylC₁-C₅alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl,    C₂-C₅dialkylaminocarbonylC₁-C₅alkyl,    C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,    N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl,    C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl    may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro),    heteroarylC₁-C₅alkyl (wherein the heteroaryl may optionally be    substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,    C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃alkylsulfonyl, halogen, cyano, or by nitro), C₂-C₅haloalkenyl,    C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or    nitro, heteroaryl or heteroaryl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by    nitro, heteroarylamino or heteroarylamino substituted by C₁-C₃    alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano    or by nitro, diheteroarylamino or diheteroarylamino substituted by    C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,    cyano or nitro, phenylamino or phenylamino substituted by    C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,    cyano or nitro, amino, hydroxyl, diphenylamino, or diphenylamino    substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,    C₁-C₃haloalkoxy, halogen, cyano or nitro, or C₃-C₇cycloalkylamino,    diC₃-C₇cycloalkylamino or C₃-C₇cycloalkoxy, C₁-C₁₀haloalkoxy,    C₁-C₅alkylamino or C₂-C₈dialkylamino, benzyloxy or phenoxy, wherein    the benzyl and phenyl groups may in turn be substituted by    C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,    cyano or nitro, and-   R^(h) is C₁-C₁₀alkyl, C₃-C₁₀alkenyl, C₃-C₁₀alkynyl, C₁-C₁₀haloalkyl,    C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₂-C₁₀aminoalkyl,    C₁-C₅alkylaminoC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl,    C₃-C₇cycloalkylC₁-C₅alkyl, C₁-C₅alkoxyC₁-C₅alkyl,    C₃-C₅alkenyloxyC₁-C₅alkyl, C₃-C₅alkynyloxyC₁-C₅alkyl,    C₁-C₅alkylthioC₁-C₅alkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl,    C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxyC₁-C₅alkyl,    C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl,    aminocarbonylC₁-C₅alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl,    C₂-C₈dialkylaminocarbonylC₁-C₅alkyl,    C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,    N—C₁-C₅alkylcarbonyl-N—C₁-C₅alkylaminoC₁-C₅alkyl,    C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl (wherein the phenyl    may optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro),    heteroarylC₁-C₅alkyl (wherein the heteroaryl may optionally be    substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,    C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃    alkylsulfonyl, halogen, cyano or by nitro), phenoxyC₁-C₅alkyl    (wherein the phenyl may optionally be substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio,    C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl, halogen, cyano or by    nitro), heteroaryloxyC₁-C₅alkyl (wherein the heteroaryl may    optionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl,    C₁-C₃ alkylsulfonyl, halogen, cyano or by nitro), C₃-C₅haloalkenyl,    C₃-C₈cycloalkyl, phenyl or phenyl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen or by nitro,    or heteroaryl, or heteroaryl substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by    nitro.

In particular, the latentiating group G is a group —C(X^(a))—R^(a) or—C(X^(b))—X^(c)—R^(b), and the meanings of X^(a), R^(a), X^(b), X^(c)and R^(b) are as defined above.

Preferably, G denotes hydrogen, an alkali metal or alkaline earth metal,where hydrogen is particularly preferred.

The latentiating group G is selected to allow its removal by one or acombination of biochemical, chemical or physical processes to affordcompounds of formula I where G is H before, during or followingapplication to the treated area or plants. Examples of these processesinclude enzymatic cleavage, chemical hydrolysis and photolysis.Compounds bearing such groups G may offer certain advantages, such asimproved penetration of the cuticula of the plants treated, increasedtolerance of crops, improved compatibility or stability in formulatedmixtures containing other herbicides, herbicide safeners, plant growthregulators, fungicides or insecticides, or reduced leaching in soils.

Preferably, R¹ is hydrogen, C₁-C₄ alkyl or C₁-C₄alkoxy and, morepreferably, R¹ is hydrogen or methyl.

Preferably, R² is hydrogen or methyl and, more preferably, R² ishydrogen.

Preferably, D is C₁-C₂alkylene or C₁-C₂alkylene substituted by C₁-C₃alkyl or C₁-C₃alkoxyC₁-C₃alkyl, in particular methylene or ethylene.

Preferably, E is optionally substituted C₁-C₂alkylene or optionallysubstituted C₂alkenylene. More preferably, E is C₁-C₂alkylene orC₁-C₂alkylene substituted by halogen, hydroxyl, cyano, C₁-C₃alkyl,C₁-C₃alkoxy or C₁-C₃alkoxyC₁-C₃alkyl, or E is C₂alkenylene orC₂alkenylene substituted by halogen, hydroxyl, cyano, C₁-C₃alkyl,C₁-C₃alkoxy or C₁-C₃alkoxyC₁-C₃alkyl, in particular, E is ethylene orethenylene.

Het is preferably an optionally substituted monocyclic 6-membered or,preferably, 5-membered sulfur or, preferably, nitrogen containingheteroaromatic ring. More preferably, Het is a monocyclic 5-memberedsulfur and nitrogen containing heteroaromatic ring, and even morepreferably, Het is a group of the formula R₁ to R₁₂

wherein

-   A designates the point of attachment to the ketoenol moiety,-   W¹ is N or CR⁶,-   W² and W³ are independently of each other N or CR⁴,-   W⁴ is N or CR⁷,-   with the proviso that at least one of W¹, W², W³ or W⁴ is N,-   X is O, S, Se, or NR⁹,-   Z is N or CR¹⁰,    wherein-   R³ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆    cycloalkyl, C₃-C₆-halocycloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl,    C₂-C₄alkynyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,    C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, nitro or cyano, preferably    halogen, C₁-C₂alkyl, C₁-C₂haloalkyl, vinyl, ethynyl, or methoxy, and    even more preferably methyl or ethyl,-   R⁴ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,    C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₃-C₆ cycloalkyl, C₅-C₆cycloalkenyl,    halogen, C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆haloalkoxy,    optionally substituted aryl, optionally substituted aryloxy,    optionally substituted heteroaryl or optionally substituted    heteroaryloxy, preferably optionally substituted aryl or optionally    substituted heteroaryl wherein the substituents are selected from    halogen, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂ haloalkyl, C₁-C₂    haloalkoxy, cyano or nitro, and even more preferably phenyl,    substituted once, twice or three times, by halogen, C₁-C₂-alkyl,    C₁-C₂-alkoxy, C₁-C₂ haloalkyl, C₁-C₂ haloalkoxy or cyano,-   R⁵ is hydrogen, C₁-C₄ alkyl, C₂-C₃alkenyl, C₂-C₃alkynyl, C₁-C₄    haloalkyl or C₂-C₃ haloalkenyl, preferably methyl or ethyl,-   R⁶ is hydrogen, methyl, halomethyl or halogen, preferably hydrogen,-   R⁷ is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄    alkenyl, C₂-C₄ haloalkenyl, C₂-C₄ alkynyl, C₁-C₄ alkoxy, C₁-C₄    haloalkoxy, C₁-C₄alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl    or cyano, preferably hydrogen, halogen, methyl or ethyl,-   R⁸ is hydrogen, methyl, ethyl, halomethyl, haloethyl, optionally    substituted aryl or optionally substituted heteroaryl, preferably    optionally substituted aryl or optionally substituted heteroaryl    wherein the substituents are selected from halogen, C₁-C₂-alkyl,    C₁-C₂-alkoxy, C₁-C₂ haloalkyl, C₁-C₂ haloalkoxy, cyano or nitro,    even more preferably phenyl, substituted once, twice or three times,    by halogen, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂ haloalkyl, C₁-C₂    haloalkoxy or cyano,-   R⁹ is hydrogen, methyl, ethyl or halomethyl, and-   R¹⁰ is hydrogen, methyl, ethyl, halomethyl, haloethyl, halogen,    cyano or nitro.

More preferably, Het is a group of the formula (R₂), wherein X is S andZ is N or CR¹⁰ and R³, R⁴ and R¹⁰ are as defined above.

The invention relates also to the salts which the compounds of formula Iare able to form with amines, alkali metal and alkaline earth metalbases or quaternary ammonium bases. Among the alkali metal and alkalineearth metal hydroxides as salt formers, special mention should be madeof the hydroxides of lithium, sodium, potassium, magnesium and calcium,but especially the hydroxides of sodium and potassium. The compounds offormula I according to the invention also include hydrates which may beformed during the salt formation.

Examples of amines suitable for ammonium salt formation include ammoniaas well as primary, secondary and tertiary C₁-C₁₈alkylamines,C₁-C₄hydroxyalkylamines and C₂-C₄-alkoxyalkylamines, for examplemethylamine, ethylamine, n-propylamine, isopropylamine, the fourbutylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,methylhexylamine, methylnonylamine, methylpentadecylamine,methyloctadecylamine, ethylbutylamine, ethylheptylamine,ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine,diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine,di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine,dioctylamine, ethanolamine, n-propanolamine, isopropanolamine,N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine,allylamine, n-but-2-enylamine, n-pent-2-enylamine,2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-enylamine,propylenediamine, trimethylamine, triethylamine, tri-n-propylamine,triisopropylamine, tri-n-butylamine, triisobutylamine,tri-sec-butylamine, tri-n-amylamine, methoxyethylamine andethoxyethylamine; heterocyclic amines, for example pyridine, quinoline,isoquinoline, morpholine, piperidine, pyrrolidine, indoline,quinuclidine and azepine; primary arylamines, for example anilines,methoxyanilines, ethoxyanilines, o-, m- and p-toluidines,phenylenediamines, benzidines, naphthylamines and o-, m- andp-chloroanilines; but especially triethylamine, isopropylamine anddiisopropylamine.

Preferred quaternary ammonium bases suitable for salt formationcorrespond, for example, to the formula [N(R′_(a)R′_(b)R′_(b)R′_(d))]OHwherein R′_(a), R′_(b), R′_(b) and R′_(d) are each independently of theothers C₁-C₄alkyl. Further suitable tetraalkylammonium bases with otheranions can be obtained, for example, by anion exchange reactions.

Depending on the nature of the substituents, compounds of formula I mayexist in different isomeric forms. When G is hydrogen, for example,compounds of formula I may exist in different tautomeric forms. Thisinvention covers all such isomers and tautomers and mixtures thereof inall proportions. Also, when substituents contain double bonds, cis- andtrans-isomers can exist. These isomers, too, are within the scope of theclaimed compounds of the formula I.

A compound of formula I wherein G is C₁-C₈ alkyl, C₂-C₈ haloalkyl,phenylC₁-C₈alkyl (wherein the phenyl may optionally be substituted byC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,C₁-C₃alkylthio, C₁-C₃alkylsufinyl, C₁-C₃ alkylsulfonyl, halogen, cyanoor by nitro), heteroarylC₁-C₈alkyl (wherein the heteroaryl mayoptionally be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃alkylsufinyl, C₁-C₃ alkylsulfonyl,halogen, cyano or by nitro), C₃-C₈ alkenyl, C₃-C₈ haloalkenyl, C₃-C₈alkynyl, C(X^(a))—R^(a), C(X^(b))—X^(c)—R^(b), C(X^(d))—N(R^(c))—R^(d),—SO₂—R^(e), —P(X^(e))(R^(f))—R^(g) or CH₂—X^(f)—R^(h) where X^(a),X^(b), X^(c), X^(d), X^(e), X^(f), R^(a), R^(b), R^(c), R^(d), R^(e),R^(f), R^(g) and R^(h) are as defined above may be prepared by treatinga compound of formula (A), which is a compound of formula I wherein G isH, with a reagent G-Z, wherein G-Z is alkylating agent such as an alkylhalide (the definition of alkyl halides includes simple C₁-C₈ alkylhalides such as methyl iodide and ethyl iodide, substituted alkylhalides such as chloromethyl alkyl ethers, Cl—CH₂—X^(f)—R^(h), whereinX^(f) is oxygen, and chloromethyl alkyl sulfides Cl—CH₂—X^(f)—R^(h),wherein X^(f) is sulfur), a C₁-C₈ alkyl sulfonate, or a di-C₁-C₈-alkylsulfate, or with a C₃-C₈ alkenyl halide, or with a C₃-C₈ alkynyl halide,or with an acylating agent such as a carboxylic acid, HO—C(X^(a))R^(a),wherein X^(a) is oxygen, an acid chloride, Cl—C(X^(a))R^(a), whereinX^(a) is oxygen, or acid anhydride, [R^(a)C(X^(a))]₂O, wherein X^(a) isoxygen, or an isocyanate, R^(c)N═C═O, or a carbamoyl chloride,Cl—C(X^(d))—N(R^(c))—R^(d) (wherein X^(d) is oxygen and with the provisothat neither R^(c) or R^(d) is hydrogen), or a thiocarbamoyl chlorideCl—C(X^(d))—N(R^(c))—R^(d) (wherein X^(d) is sulfur and with the provisothat neither R^(c) or R^(d) is hydrogen) or a chloroformate,Cl—C(X^(b))—X^(c)—R^(b), (wherein X^(b) and X^(c) are oxygen), or achlorothioformate Cl—C(X^(b))—X^(c)—R^(b) (wherein X^(b) is oxygen andX^(c) is sulfur), or a chlorodithioformate Cl—C(X^(b))—X^(c)—R^(b),(wherein X^(b) and X^(c) are sulfur), or an isothiocyanate, R^(c)N═C═S,or by sequential treatment with carbon disulfide and an alkylatingagent, or with a phosphorylating agent such as a phosphoryl chloride,Cl—P(X^(e))(R^(f))—R^(g) or with a sulfonylating agent such as asulfonyl chloride Cl—SO₂—R^(e), preferably in the presence of at leastone equivalent of base.

Where substituents R¹ and R² are different, these reactions may produce,in addition to a compound of formula I, a second compound of formula IA.This invention covers both a compound of formula I and a compound offormula IA, together with mixtures of these compounds in any ratio.

The O-alkylation of cyclic 1,3-diones is known; suitable methods aredescribed, for example, in U.S. Pat. No. 4,436,666. Alternativeprocedures have been reported by M. T. Pizzorno and S. M. Albonico,Chem. Ind. (London), (1972), 425-426; H. Born et al., J. Chem. Soc.,(1953), 1779-1782; M. G. Constantino et al., Synth. Commun., (1992), 22(19), 2859-2864; Y. Tian et al., Synth. Commun., (1997), 27 (9),1577-1582; S. Chandra Roy et al., Chem. Letters, (2006), 35 (1), 16-17;P. K. Zubaidha et al., Tetrahedron Lett., (2004), 45, 7187-7188.

The O-acylation of cyclic 1,3-diones may be effected by proceduressimilar to those described, for example, in U.S. Pat. Nos. 4,175,135,4,422,870, 4,659,372 and 4,436,666. Typically diones of formula (A) maybe treated with the acylating agent in the presence of at least oneequivalent of a suitable base, optionally in the presence of a suitablesolvent. The base may be inorganic, such as an alkali metal carbonate orhydroxide, or a metal hydride, or an organic base such as a tertiaryamine or metal alkoxide. Examples of suitable inorganic bases includesodium carbonate, sodium or potassium hydroxide, sodium hydride, andsuitable organic bases include trialkylamines, such as trimethylamineand triethylamine, pyridines or other amine bases such as1,4-diazobicyclo[2.2.2]octane and 1,8-diazabicyclo[5.4.0]undec-7-ene.Preferred bases include triethylamine and pyridine. Suitable solventsfor this reaction are selected to be compatible with the reagents andinclude ethers such as tetrahydrofuran and 1,2-dimethoxyethane andhalogenated solvents such as dichloromethane and chloroform. Certainbases, such as pyridine and triethylamine, may be employed successfullyas both base and solvent. For cases where the acylating agent is acarboxylic acid, acylation is preferably effected in the presence of acoupling agent such as 2-chloro-1-methylpyridinium iodide,N,N′-dicyclohexylcarbodiimide,1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and N,N′-carbodiimidazole,and optionally a base such as triethylamine or pyridine in a suitablesolvent such as tetrahydrofuran, dichloromethane or acetonitrile.Suitable procedures are described, for example, by W. Zhang and G. Pugh,Tetrahedron Lett., (1999), 40 (43), 7595-7598 and T. Isobe and T.Ishikawa, J. Org. Chem., (1999), 64 (19), 6984.

Phosphorylation of cyclic 1,3-diones may be effected using a phosphorylhalide or thiophosphoryl halide and a base by procedures analogous tothose described in U.S. Pat. No. 4,409,153.

Sulfonylation of a compound of formula (A) may be achieved using analkyl or aryl sulfonyl halide, preferably in the presence of at leastone equivalent of base, for example by the procedure of C. J. Kowalskiand K. W. Fields, J. Org. Chem., (1981), 46, 197. Compounds of formula(A) may be prepared via the cyclisation of compounds of formula (B),preferably in the presence of an acid or base, and optionally in thepresence of a suitable solvent, by analogous methods to those describedin U.S. Pat. No. 4,209,532. The compounds of the formula (B) have beenparticularly designed as intermediates in the synthesis of the compoundsof the formula I. Compounds of formula (B) wherein R is hydrogen may becyclised under acidic conditions, preferably in the presence of a strongacid such as sulfuric acid, polyphosphoric acid or Eaton's reagent,optionally in the presence of a suitable solvent such as acetic acid,toluene or dichloromethane.

Compounds of formula (B) wherein R is alkyl (preferably methyl or ethyl)may be cyclised under acidic or basic conditions, preferably in thepresence of at least one equivalent of a strong base such as potassiumtert-butoxide, lithium diisopropylamide or sodium hydride and in asolvent such as tetrahydrofuran, toluene, dimethylsulfoxide orN,N-dimethylformamide.

Compounds of formula (B), wherein R is H may be prepared bysaponification of compounds of formula (C) wherein R′ is alkyl(preferably methyl or ethyl) under standard conditions, followed byacidification of the reaction mixture to effect decarboxylation, bysimilar processes to those described, for example, in U.S. Pat. No.4,209,532:

Compounds of formula (B), wherein R is H may be esterified to compoundsof formula (B), wherein R is alkyl, under standard conditions.

Compounds of formula (C) wherein R is alkyl may be prepared by treatingcompounds of formula (D) with suitable carboxylic acid chlorides offormula (E) wherein R is alkyl under basic conditions. Suitable basesinclude potassium tert-butoxide, sodium bis(trimethylsilyl)amide andlithium diisopropylamide and the reaction is preferably conducted in asuitable solvent (such as tetrahydrofuran or toluene) at a temperatureof between −80° C. and 30° C.:

Alternatively, compounds of formula (C), wherein R is H, may be preparedby treating compounds of formula (D) with a suitable base (such aspotassium tert-butoxide, sodium bis(trimethylsilyl)amide and lithiumdiisopropylamide) in a suitable solvent (such as tetrahydrofuran ortoluene) at a suitable temperature (between −80° C. and 0° C.) andreacting the resulting anion with a suitable anhydride of formula (F):

Compounds of formula (D) are known, or may be made by known methods fromknown compounds (see, for example, E. Bellur and P. Langer, Synthesis(2006), 3, 480-488; E. Bellur and P. Langer, Eur. J. Org. Chem., (2005),10, 2074-2090; G. Bartolo et al., J. Org. Chem., (1999), 64 (21),7693-7699; R. Kranich et al., J. Med. Chem., (2007), 50 (6), 1101-1115;I. Freifeld et al., J. Org. Chem., (2006) 71 (13), 4965-4968; S. Hermannet al., WO2006/087120; R. Fischer et al. WO96/16061; H. A. Staab and G.A. Schwalbach, Justus Liebigs Annalen der Chemie, (1968), 715, 128-34;J-L Brayer et al., EP402246; P. Chemla et al., WO99/32464; A. Dornow andG. Petsch, Chem. Berichte, (1953), 86, 1404-1407; E. Y-H Chao et al.,WO2001/000603; D. B. Lowe et al., WO2003/011842; R. Fischer et al.,WO2001/096333; J. Ackermann et al., WO2005/049572; B. Li et al., Bioorg.Med. Chem. Lett., (2002), 12, 2141-2144, G. P. Rizzi, J. Org. Chem.,(1968), 33 (4) 13333-13337; M. Okitsu and K. Yoshid, JP63230670; F.Bohlmann et al., Chem. Ber., (1955), 88, 1831-1838; R. Fischer et al.,WO2003/035463; R. Fischer et al., WO2005/005428; D O'Mant, GB1226981).

Compounds of formula (E) and formula (F) are known (see, for example, K.Crowley, J. Am. Chem. Soc., (1964), Vol. 86, No. 24, 5692-5693; E.Bercot and T. Rovis, J. Am. Chem. Soc., 2005, 127, 247-254; R. McDonaldand R. Reitz, J. Am. Chem. Soc., (1976), Vol. 98, No. 25, 8144-8155; A.Smith III et al., J. Org. Chem., (1974), Vol. 39, No. 12, 1607-1612; J.Baldwin and M. Lusch, J. Org. Chem., (1979), Vol. 44, No. 12, 1923-1927;R. Carlson and K. May, Tetrahedron Lett., (1975), Vol. 16, No. 11,947-950; A. Börner et al., Tetrahedron Asymmetry (2002), 13, 1615-1620)or may be made by similar methods from commercially available startingmaterials.

In a further approach to compounds of formula (A), a compound of formula(G), which is a compound of formula (A) wherein Het is (R₂) when R³ isCH₂R″ and R″ is hydrogen, alkyl or halogenoalkyl (preferably hydrogen,methyl or trifluoromethyl), may be prepared by thermal rearrangement ofa compound of formula (H), optionally in the presence of a suitablesolvent and optionally under microwave irradiation.

Preferably, the rearrangement is effected by heating a compound offormula (H) at temperatures of between 120-300° C., optionally in asuitable solvent such as 1,2-dimethoxyethane, diethylene glycol dimethylether, triethylene glycol dimethyl ether, tetraethylene glycol dimethylether, xylene, mesitylene or Dowtherm®, and optionally under microwaveirradiation.

Similarly, a compound of formula (J), which is a compound of formula (A)wherein Het is (R₃) when R³ is CH₂R″ and R″ is hydrogen, alkyl orhalogenoalkyl (preferably hydrogen, methyl or trifluoromethyl), may beprepared from a compound of formula (K) using similar methods.

A compound of formula (H) may be prepared from a compound of formula (L)by alkylation with a compound of formula (M), wherein L is a suitableleaving group such as a halogen or an alkyl- or aryl-sulfonate,optionally in the presence of a suitable base and optionally in asuitable solvent as described above for the alkylation of compounds offormula (A)

Similarly, a compound of formula (K) may be prepared from a compound offormula (L) by alkylation with a compound of formula (N), wherein Lisasuitable leaving group such as a halogen or an alkyl- or aryl-sulfonate,under similar conditions.

In an alternative approach, a compound of formula (H) may be preparedfrom a compound of formula (L) by condensation with an alcohol offormula (O), optionally in the presence of a suitable acid catalyst suchas p-toluenesulfonic acid, or a Lewis acid catalyst, for example,ytterbium (III) trifluoromethanesulfonate, lanthanum (III)trifluoromethanesulfonate, sodium tetrachloroaurate (III) dihydrate,titanium (IV) chloride, indium (III) chloride or aluminium chloride, andoptionally in a suitable solvent. Suitable solvents are selected to becompatible with the reagents used, and include, for example, toluene,ethanol or acetonitrile. Similar approaches have been described by, forexample, M. Curini; F. Epifano, S. Genovese, Tetrahedron Lett., (2006),47, 4697-700; A. Arcadi, G. Bianchi, S. Di Giuseppe, and by F.Marinelli, Green Chemistry, (2003), 5, 64-7.

Alternatively, the condensation may be effected in the presence ofsuitable coupling agents such as 2-chloro-1-methylpyridinium iodide,N,N′-dicyclohexylcarbodiimide,1,(3-dimethylaminopropyl)-3-ethylcarbodiimide and N,N-carbodiimidazoleand optionally a suitable base such a triethylamine or pyridine in asuitable solvent such as tetrahydrofuran, acetonitrile ordichloromethane, or in the presence of a triarylphosphine (such astriphenylphosphine) and a dialkyl azidodicarboxylate (preferably diethylazidodicarboxylate or diisopropyl azidodicarboxylate) and in a suitablesolvent such as diethyl ether, tetrahydrofuran or 1,4-dioxane asdescribed, for example, by O. Mitsunobu, Synthesis (1981), 1, 1-28.

Using similar processes, a compound of formula (K) may be prepared byreaction of a compound of formula (L) with a compound of formula (P).

Additional compounds of formula (H) wherein R⁴ is an aromatic orheteroaromatic moiety, or is an alkyl, alkenyl or alkynyl group, may beprepared by the reaction of a compound of formula (Q), wherein Q is anatom or group suitable for undergoing cross-coupling reactions (forexample Q is chlorine, bromine or iodine, or a haloalkylsulfonate suchas trifluoromethanesulfonate), and R″ is as defined for a compound offormula (G), with a suitable coupling partner under conditions describedin the literature for Suzuki-Miyaura, Sonogashira, Stille and relatedcross-coupling reactions.

For example, a compound of formula (Q) may be treated with an aryl-,heteroaryl-, alkyl-, alkenyl- or alkynylboronic acid, R⁴—B(OH)₂,boronate ester, R⁴—B(OR′″)₂, wherein R′″ is C₁-C₆alkyl or R⁴—B(OR′″)₂represents a cyclic boronate ester derived from a C₁-C₆diol (especiallypreferred are cyclic boronate esters derived from pinacol), or a metal(especially potassium) aryl-, heteroaryl, alkyl-, alkenyl- andalkynyltrifluoroborate salt, M⁺[R⁴—BF₃]⁻ in the presence of a suitablepalladium catalyst, a suitable ligand and a suitable base in thepresence of a suitable solvent, under Suzuki-Miyaura conditions (see,for example K. Billingsley and S. Buchwald, J. Am. Chem. Soc., (2007),129, 3358-3366; H. Stefani, R. Cella and A. Vieira, Tetrahedron, (2007),63, 3623-3658; N. Kudo, M. Perseghini and G. Fu, Angew. Chem. Int. Ed.,(2006), 45, 1282-1284; A. Roglans, A. Pla-Quintana and M. Moreno-Mañas,Chem. Rev., (2006), 106, 4622-4643; J-H Li, Q-M Zhu and Y-X Xie,Tetrahedron (2006), 10888-10895; S, Nolan et al., J. Org. Chem., (2006),71, 685-692; M. Lysén and K. Köhler, Synthesis, (2006), 4, 692-698; K.Anderson and S. Buchwald, Angew. Chem. Int. Ed., (2005), 44, 6173-6177;Y. Wang and D. Sauer, Org. Lett., (2004), 6 (16), 2793-2796; I.Kondolff, H. Doucet and M, Santelli, Tetrahedron, (2004), 60, 3813-3818;F. Bellina, A. Carpita and R. Rossi, Synthesis (2004), 15, 2419-2440; H.Stefani, G. Molander, C-S Yun, M. Ribagorda and B. Biolatto, J. Org.Chem., (2003), 68, 5534-5539; A. Suzuki, Journal of OrganometallicChemistry, (2002), 653, 83; G. Molander and C-S Yun, Tetrahedron,(2002), 58, 1465-1470; G. Zou, Y. K. Reddy and J. Falck, TetrahedronLett., (2001), 42, 4213-7215; S. Darses, G. Michaud and J-P, Genet, Eur.J. Org. Chem., (1999), 1877-1883).

Alternatively, a compound of formula (H), wherein R⁴ is an optionallysubstituted acetylene, may be prepared from a compound of formula (Q) byreacting with a terminal alkyne, R⁴—H, in the presence of a suitablepalladium catalyst and optionally in the presence of a suitable copperco-catalyst, a suitable ligand, a suitable base and a suitable additiveunder conditions known to effect the Sonogashira coupling (see, forexample, U. Sorenson and E Pombo-Villar, Tetrahedron, (2005), 2697-2703;N. Leadbeater and B. Tominack, Tetrahedron Lett., (2003), 44, 8653-8656;K. Sonogashira, J. Organomet. Chem., (2002), 653, 46-49).

In a further approach, a compound of formula (H), wherein R⁴ is alkyl,optionally substituted vinyl, optionally substituted ethynyl, optionallysubstituted aryl or optionally substituted heteroaryl, may be preparedfrom a compound of formula (Q) by reaction with a suitableorganostannane under Stille conditions (see, for example, R. Bedford, C.Cazin and S. Hazlewood, (2002), 22, 2608-2609; S. Ley et al., Chem.Commun., (2002), 10, 1134-1135; G. Grasa and S, Nolan, Org. Lett.,(2001), 3 (1), 119-122; T. Weskamp, V. Boehm, J. Organomet. Chem.,(1999), 585 (2), 348-352; A. Littke and G. Fu, Angew. Chem. Int. Ed.,(1999), 38 (16), 2411-2413; J. Stille et al., Org. Synth., (1992), 71,97).

A compound of formula (K) may be prepared from a compound of formula(R), wherein Q and R″ are as defined for a compound of formula (Q), byanalogous methods using appropriate starting materials.

A compound of formula (Q) may be prepared from a compound of formula(L), by reaction with a compound of formula (S) wherein L is a suitableleaving group such as a halogen or an alkyl- or aryl-sulfonate, byprocesses analogous to those described above for the preparation of acompound of formula (H) from a compound of formula (L). Alternatively, acompound of formula (Q) may be prepared by reaction of a compound offormula (L) with a compound of formula (T) by processes analogous tothose described above for the preparation of a compound of formula (H)from a compound of formula (L).

By analogous processes to those described above, a compound of formula(R) may be prepared from a compound of formula (L) by alkylation with acompound of formula (U), wherein L is a suitable leaving group such as ahalogen or an alkyl- or aryl-sulfonate, or by alkylation with a compoundof formula (V).

In an alternative approach, a compound of formula (L) may be treatedwith a halogenating agent such as phosphorus oxychloride, phosphoruspentachloride, phosphorus pentabromide, phosphorus oxybromide, oxalylchloride or oxalyl bromide, optionally in a suitable solvent such astoluene, chloroform, dichloromethane and optionally in the presence ofN,N-dimethylformamide, and the resulting vinyl halide of formula (W),wherein Hal is chlorine or bromine may be converted by reaction with analcohol of formula (O), or of formula (P), or of formula (T) or offormula (V) optionally in the presence of a suitable base such as sodiumhydride, sodium tert-butoxide, potassium tert-butoxide and optionally ina suitable solvent such as tetrahydrofuran, 1,4-dioxane, diethyleneglycol dimethyl ether to give a compound of formula (H), formula (K),formula (Q) and formula (R) respectively:

Compounds of formula (L) are known compounds or may be prepared byroutes analogous to those described in the literature (see, for example,S. Spessard and B. Stoltz, Organic Letters, (2002), Vol. 4, No. 11,1943-1946; F. Effenberger et al., Chem. Ber., (1984), 117, 3280-3296; W.Childers, Jr. et al., Tetrahedron Lett., (2006), 2217-2218; H. Schneiderand C. Luethy, EP1352890; D. Jackson, A. Edmunds, M. Bowden and B.Brockbank, WO2005105745 and WO2005105717; R. Beaudegnies, C. Luethy, A.Edmunds, J. Schaetzer and S. Wendeborn, WO2005123667; J-C. Beloeil, J-Y.Lallemand, T. Prange, Tetrahedron, (1986), Vol. 42. No. 13, 3491-3502).

Compounds of formula (M), formula (N), formula (O), formula (P), formula(S), formula (T), formula (U) and formula (V) are known or may beprepared by known methods from known compounds (see, for example T. T.Denton, X. Zhang, J. R. Cashman, J. Med. Chem., (2005), 48, 224-239; J.Reinhard, W. E. Hull, C.-W. von der Lieth, U. Eichhorn, H.-C. Kliem, J.Med. Chem., (2001), 44, 4050-4061; H. Kraus and H. Fiege, DE19547076; M.L. Boys, L. A. Schretzman, N. S. Chandrakumar, M. B. Tollefson, S. B.Mohler, V. L. Downs, T. D. Penning, M. A. Russell, J. A. Wendt, B. B.Chen, H. G. Stenmark, H. Wu, D. P. Spangler, M. Clare, B. N. Desai, I.K. Khanna, M. N. Nguyen, T. Duffin, V. W. Engleman, M. B. Finn, S. K.Freeman, M. L. Hanneke, J. L. Keene, J. A. Klover, G. A. Nickols, M. A.Nickols, C. N. Steininger, M. Westlin, W. Westlin, Y. X. Yu, Y. Wang, C.R. Dalton, S. A. Norring, Bioorg. Med. Chem. Lett., (2006), 16, 839-844;A. Silberg, A. Benko, G. Csavassy, Chem. Ber., (1964), 97, 1684-1687; K.Brown and R. Newbury, Tetrahedron Lett., (1969), 2797; A. Jansen and M.Szelke, J. Chem. Soc., (1961), 405; R. Diaz-Cortes, A. Silva and L.Maldonado, Tetrahedron Lett., (1997), 38(13), 2007-2210; M. Friedrich,A. Waechtler and A De Meijure, Synlett., (2002), 4, 619-621; F. Kerdeskyand L. Seif, Synth. Commun., (1995), 25 (17), 2639-2645; Z. Zhao, G.Scarlato and R. Armstrong., Tetrahedron Lett., (1991), 32 (13),1609-1612; K-T. Kang and S. Jong, Synth. Commun. (1995), (17),2647-2653; M. Altamura and E. Perrotta, J. Org. Chem., (1993), 58 (1),272-274).

In a further approach, a compound of formula (A) may be prepared byreaction of a compound of formula (L) with a heteroaryl leadtricarboxylate under conditions described in the literature (for examplesee, J. T. Pinhey, B. A. Rowe, Aust. J. Chem., (1979), 32, 1561-6; J.Morgan, J. T. Pinhey, J. Chem. Soc. Perkin Trans. 1, (1990), 3, 715-20;J. T. Pinhey, Roche, E. G. J. Chem. Soc. Perkin Trans. 1, (1988),2415-21). Preferably the heteroaryl lead tricarboxylate is a heteroaryltriacetate of formula (X) and the reaction is conducted in the presenceof a suitable ligand (for example N,N-dimethylaminopyridine, pyridine,imidazole, bipyridine, and 1,10-phenanthroline, preferably one to tenequivalents of N,N-dimethylaminopyridine with respect to compound (L))and in a suitable solvent (for example chloroform, dichloromethane andtoluene, preferably chloroform and optionally in the presence of aco-solvent such as toluene) at 25° C. to 100° C. (preferably 60-90° C.).

A compound of formula (X) may be prepared from a compound of formula (Y)by treatment with lead tetraacetate in a suitable solvent (for examplechloroform) at 25° C. to 100° C. (preferably 25-50° C.), optionally inthe presence of a catalyst such as mercury diacetate, according toprocedures described in the literature (for example see, K. Shimi, G.Boyer, J-P. Finet and J-P. Galy, Letters in Organic Chemistry, (2005),2, 407-409; J. Morgan and J. T. Pinhey, J. Chem. Soc. Perkin Trans. 1;(1990), 3, 715-20).

Suitable boronic acids include heteroarylboronic acids, (Y₁) to (Y₈),wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, X, W¹, W², W³, W⁴ and Z are as definedabove.

Heteroarylboronic acids of formula (Y) are known compounds, or may beprepared from known compounds by known methods (see for example A.Voisin et al., Tetrahedron (2005); 1417-1421; A. Thompson et al,Tetrahedron (2005), 61, 5131-5135; K. Billingsley and S. Buchwald, J.Am. Chem. Soc., (2007), 129, 3358-3366; N. Kudo, M. Pauro and G. Fu,Angew. Chem. Int. Ed., (2006), 45, 1282-1284; A. Ivachtchenko et al., J.Heterocyclic Chem., (2004), 41(6), 931-939; H. Matondo et al., Synth.Commun., (2003), 33 (5) 795-800; A. Bouillon et al., Tetrahedron,(2003), 59, 10043-10049; W. Li et al., J. Org. Chem., (2002), 67,5394-5397; C. Enguehard et al., J. Org. Chem. (2000), 65, 6572-6575; H-NNguyen, X. Huang and S. Buchwald, J. Am. Chem. Soc., (2003), 125,11818-11819, and references therein).

In a further approach, a compound of formula (A) may be prepared fromcompounds of formula (Z) by reaction with a heteroaryl boronic acid offormula (Y), in the presence of a suitable palladium catalyst and abase, and preferably in a suitable solvent.

Suitable palladium catalysts are generally palladium(II) or palladium(0)complexes, for example palladium(II) dihalides, palladium(II) acetate,palladium(II) sulfate, bis(triphenylphosphine)palladium(II) dichloride,bis(tricyclopentylphosphine)palladium(II) dichloride,bis(tricyclohexylphosphine)palladium(II) dichloride,bis(dibenzylideneacetone)palladium(0) ortetrakis(triphenylphosphine)palladium(0). The palladium catalyst canalso be prepared “in situ” from palladium(II) or palladium(0) compoundsby complexing with the desired ligands, by, for example, combining thepalladium(II) salt to be complexed, for example palladium(II) dichloride(PdCl₂) or palladium(II) acetate (Pd(OAc)₂), together with the desiredligand, for example triphenylphosphine (PPh₃), tricyclopentylphosphineor tricyclohexylphosphine and the selected solvent, with a compound offormula (Z), a heteroaromatic boronic acid of formula (Y) and a base.Also suitable are bidendate ligands, for example1,1′-bis(diphenylphosphino)ferrocene or1,2-bis(diphenylphosphino)ethane. By heating the reaction medium, thepalladium(II) complex or palladium(0) complex desired for the C—Ccoupling reaction is thus formed “in situ”, and then initiates the C—Ccoupling reaction. The palladium catalysts are used in an amount of from0.001 to 50 mol %, preferably in an amount of from 0.1 to 15 mol %,based on the compound of formula (Z). More preferably the palladiumsource is palladium acetate, the base is lithium hydroxide and thesolvent is a mixture of 1,2-dimethoxyethane and water in a ratio of 4:1to 1:4. The reaction may also be carried out in the presence of otheradditives, such as tetralkylammonium salts, for example,tetrabutylammonium bromide:

A compound of formula (Z) may be prepared from a compound of formula (L)by treatment with (diacetoxy)iodobenzene according to the procedures ofK. Schank and C. Lick, Synthesis, (1983), 392, or of Z Yang et al., Org.Lett., (2002), 4 (19), 3333:

In a further approach, a compound of formula (A) may be prepared from acompound of formula I or IA (wherein G is C₁₋₄ alkyl) by hydrolysis,preferably in the presence of an acid catalyst such as hydrochloric acidand optionally in the presence of a suitable solvent such astetrahydrofuran. A compound of formula I (wherein G is C₁₋₄ alkyl) maybe prepared by reacting a compound of formula (AA) (wherein G is C₁₋₄alkyl, and Hal is a halogen, preferably bromine or iodine), with aheteroaryl boronic acid, Het-B(OH)₂, of formula (Y) in the presence of asuitable palladium catalyst (for example 0.001-50% palladium(II) acetatewith respect to compound (AA)) and a base (for example 1 to 10equivalents potassium phosphate with respect to compound (AA)) andpreferably in the presence of a suitable ligand (for example 0.001-50%(2-dicyclohexylphosphino)-2′,6′-dimethoxybiphenyl with respect tocompound (AA)), and in a suitable solvent (for example toluene),preferably between 25° C. and 200° C. Similar couplings are known in theliterature (see for example, Y. S. Song, B. T. Kim and J.-N. Heo,Tetrahedron Letters (2005), 46(36), 5987-5990).

A compound of formula (AA) may be prepared by halogenating a compound offormula (L), followed by alkylation of the resulting halide of formula(BB) with a C₁₋₄ alkyl halide or tri-C₁₋₄-alkylorthoformate under knownconditions, for example by the procedures of R. G. Shepherd and A. C.White (J. Chem. Soc. Perkin Trans. 1 (1987), 2153-2155) and Y.-L. Lin etal. (Bioorg. Med. Chem. (2002), 10, 685-690). Alternatively, a compoundof formula (AA) may be prepared by alkylating a compound of formula (L)with a C₁₋₄ alkyl halide or a tri-C₁₋₄-alkylorthoformate, andhalogenating the resulting enone of formula (CC) under known conditions(see for example Y. S. Song, B. T. Kim and J.-N. Heo, TetrahedronLetters (2005), 46(36), 5987-5990).

In a further approach, a compound of formula (A) may be prepared byreacting a compound of formula (L) with a suitable heteroaryl halide(such as an iodide or bromide), Het-hal, in the presence of a suitablepalladium catalyst (for example 0.001-50% palladium(II) acetate withrespect to compound (L)) and a base (for example 1 to 10 equivalentspotassium phosphate with respect to compound (L)) and preferably in thepresence of a suitable ligand (for example 0.001-50%(2-dicyclohexylphosphino)-2′,4′,6′-triisopropylbiphenyl with respect tocompound (L)), and in a suitable solvent (for example dioxane),preferably between 25° C. and 200° C. Similar couplings are known in theliterature (see for example, J. M. Fox, X. Huang, A. Chieffi, and S. L.Buchwald, J. Am. Chem. Soc. (2000), 122, 1360-1370; B. Hong et al. WO2005/000233). Alternatively, a compound of formula (A) may be preparedby reacting a compound of formula (L) with a suitable heteroaryl halide(such as an iodide or bromide), Het-hal, in the presence of a suitablecopper catalyst (for example 0.001-50% copper(I) iodide with respect tocompound (L)) and a base (for example 1 to 10 equivalents potassiumcarbonate with respect to compound (L)) and preferably in the presenceof a suitable ligand (for example 0.001-50% L-proline with respect tocompound (L)), and in a suitable solvent (for exampledimethylsulfoxide), preferably between 25° C. and 200° C. Similarcouplings are known in the literature for aryl halides (see for example,Y. Jiang, N. Wu, H. Wu, and M. He, Synlett, (2005), 18, 2731-2734).

Those skilled in the art will appreciate that compounds of formula I maycontain a heteroaromatic moiety bearing one or more substituents capableof being transformed into alternative substituents under knownconditions, and that these compounds may themselves serve asintermediates in the preparation of additional compounds of formula I.For example, a heterocycle of formula (G) wherein R⁴ is alkenyl oralkynyl, may be reduced to a compound of formula (G) wherein R⁴ is alkylunder known conditions.

Furthermore, a compound of formula (EE) wherein Q is an atom or groupsuitable for cross-coupling chemistry (such as a halogen or ahaloalkylsulfonate) may undergo Suzuki-Miyaura, Stille, Sonogashira andrelated reactions under known conditions to give additional compounds offormula G. A compound of formula (EE) may be prepared by rearranging acompound of formula (Q) under conditions similar to those used toconvert a compound of formula (H) to a compound of formula (G):

Those skilled in the art will appreciate that transformations of thistype are not restricted to compounds of formula (EE), but may in generalbe applied to any compound of formula I where Het is a heterocyclesubstituted by an atom or group suitable for further derivatisation.

In a further approach to compounds of formula (A), wherein Het is agroup of formula (R₂), X is S, and Y is N, a compound of formula (FF)wherein L is a suitable leaving group such as a halogen or an alkyl- orhaloalkylsulfonate, may be treated with a compound of formula (GG),optionally in the presence of a suitable base (such as triethylamine orpyridine), and optionally in a suitable solvent (such as water, toluene,acetone, ethanol or isopropanol) according to known procedures, (see,for example, E. Knott, J. Chem. Soc., (1945), 455; H. Brederick, R.Gompper, Chem. Ber. (1960), 93, 723; B. Friedman, M. Sparks and R.Adams, J. Am. Chem. Soc., (1937), 59, 2262).

Alternatively, a compound of formula (FF) may be treated with thiourea,by known procedures (see, for example, V. Pshenichniya, O. Gulyakevichand V. Kripach, Chemistry of Heterocyclic Compounds, (1990), 10,1409-1412), and the resulting product of formula (HH) may be convertedinto additional compounds of formula (A) by conversion to a halide offormula (II), wherein Hal is chlorine, bromine or iodine, underSandmeyer conditions, and a compound of formula (II) may be converted tocompounds of formula (A) by cross-coupling under known conditions forthe Suzuki-Miyaura, Sonogashira, Stille and related reactions, asdescribed previously.

A compound of formula (FF) may be prepared from a compound of formula(L) under known conditions (see, for example, V. Pshenichniya, O.Gulyakevich and V. Kripach, Chemistry of Heterocyclic Compounds, (1990),10, 1409-1412; V. Pshenichniya, O. Gulyakevich and V. Kripach, RussianJournal of Organic Chemistry, (1989), 25 (9), 1882-1888).

The compounds of formula I according to the invention can be used asherbicides in unmodified form, as obtained in the synthesis, but theyare generally formulated into herbicidal compositions in a variety ofways using formulation adjuvants, such as carriers, solvents andsurface-active substances. The formulations can be in various physicalforms, for example in the form of dusting powders, gels, wettablepowders, water-dispersible granules, water-dispersible tablets,effervescent compressed tablets, emulsifiable concentrates,microemulsifiable concentrates, oil-in-water emulsions, oil flowables,aqueous dispersions, oily dispersions, suspoemulsions, capsulesuspensions, emulsifiable granules, soluble liquids, water-solubleconcentrates (with water or a water-miscible organic solvent ascarrier), impregnated polymer films or in other forms known, forexample, from the Manual on Development and Use of FAO Specificationsfor Plant Protection Products, 5th Edition, 1999. Such formulations caneither be used directly or are diluted prior to use. Dilutedformulations can be prepared, for example, with water, liquidfertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared, for example, by mixing the activeingredient with formulation adjuvants in order to obtain compositions inthe form of finely divided solids, granules, solutions, dispersions oremulsions. The active ingredients can also be formulated with otheradjuvants, for example finely divided solids, mineral oils, vegetableoils, modified vegetable oils, organic solvents, water, surface-activesubstances or combinations thereof. The active ingredients can also becontained in very fine microcapsules consisting of a polymer.Microcapsules contain the active ingredients in a porous carrier. Thisenables the active ingredients to be released into their surroundings incontrolled amounts (e.g. slow release). Microcapsules usually have adiameter of from 0.1 to 500 microns. They contain active ingredients inan amount of about from 25 to 95% by weight of the capsule weight. Theactive ingredients can be present in the form of a monolithic solid, inthe form of fine particles in solid or liquid dispersion or in the formof a suitable solution. The encapsulating membranes comprise, forexample, natural and synthetic gums, cellulose, styrene-butadienecopolymers, polyacrylonitrile, polyacrylate, polyester, polyamides,polyureas, polyurethane or chemically modified polymers and starchxanthates or other polymers that are known to the person skilled in theart in this connection. Alternatively it is possible for very finemicrocapsules to be formed wherein the active ingredient is present inthe form of finely divided particles in a solid matrix of a basesubstance, but in that case the microcapsule is not encapsulated.

The formulation adjuvants suitable for the preparation of thecompositions according to the invention are known per se. As liquidcarriers there may be used: water, toluene, xylene, petroleum ether,vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acidanhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,butylenes carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkylesters of acetic acid, diacetone alcohol, 1,2-dichloropropane,diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycolabietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methylether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,ethyl acetate, 2-ethyl hexanol, ethylene carbonate,1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyllactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycolmethyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glyceroldiacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,isopropyl myristate, lactic acid, laurylamine, mesityl oxide,methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyllaurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene,n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleicacid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG 400),propionic acid, propyl lactate, propylene carbonate, propylene glycol,propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate,triethylene glycol, xylenesulfonic acid, paraffin, mineral oil,trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butylacetate, propylene glycol methyl ether, diethylene glycol methyl ether,methanol, ethanol, isopropanol, and higher molecular weight alcohols,such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol,ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone andthe like. Water is generally the carrier of choice for the dilution ofthe concentrates. Suitable solid carriers are, for example, talc,titanium dioxide, pyrophyllite clay, silica, attapulgite clay,kieselguhr, limestone, calcium carbonate, bentonite, calciummontmorillonite, cottonseed husks, wheatmeal, soybean flour, pumice,wood flour, ground walnut shells, lignin and similar materials, asdescribed, for example, in CFR 180.1001. (c) & (d).

A large number of surface-active substances can advantageously be usedboth in solid and in liquid formulations, especially in thoseformulations which can be diluted with a carrier prior to use.Surface-active substances may be anionic, cationic, non-ionic orpolymeric and they may be used as emulsifiying, wetting or suspendingagents or for other purposes. Typical surface-active substances include,for example, salts of alkyl sulfates, such as diethanolammonium laurylsulfate; salts of alkylarylsulfonates, such as calciumdodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products,such as nonylphenol ethoxylate; alcohol-alkylene oxide additionproducts, such as tridecyl alcohol ethoxylate; soaps, such as sodiumstearate; salts of alkylnaphthalenesulfonates, such as sodiumdibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts,such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such assorbitol oleate; quaternary amines, such as lauryl trimethylammoniumchloride, polyethylene glycol esters of fatty acids, such aspolyethylene glycol stearate; block copolymers of ethylene oxide andpropylene oxide; and salts of mono- and di-alkyl phosphate esters; andalso further substances described e.g. in “McCutcheon's Detergents andEmulsifiers Annual”, MC Publishing Corp., Ridgewood, N.J., 1981.

Further adjuvants which can usually be used in pesticidal formulationsinclude crystallisation inhibitors, viscosity-modifying substances,suspending agents, dyes, anti-oxidants, foaming agents, light absorbers,mixing aids, anti-foams, complexing agents, neutralising or pH-modifyingsubstances and buffers, corrosion-inhibitors, fragrances, wettingagents, absorption improvers, micronutrients, plasticisers, glidants,lubricants, dispersants, thickeners, anti-freezes, microbiocides, andalso liquid and solid fertilisers.

The formulations may also comprise additional active substances, forexample further herbicides, herbicide safeners, plant growth regulators,fungicides or insecticides.

The compositions according to the invention can additionally include anadditive comprising an oil of vegetable or animal origin, a mineral oil,alkyl esters of such oils or mixtures of such oils and oil derivatives.The amount of oil additive used in the composition according to theinvention is generally from 0.01 to 10%, based on the spray mixture. Forexample, the oil additive can be added to the spray tank in the desiredconcentration after the spray mixture has been prepared. Preferred oiladditives comprise mineral oils or an oil of vegetable origin, forexample rapeseed oil, olive oil or sunflower oil, emulsified vegetableoil, such as AMIGO® (Rhone-Poulenc Canada Inc.), alkyl esters of oils ofvegetable origin, for example the methyl derivatives, or an oil ofanimal origin, such as fish oil or beef tallow. A preferred additivecontains, for example, as active components essentially 80% by weightalkyl esters of fish oils and 15% by weight methylated rapeseed oil, andalso 5% by weight of customary emulsifiers and pH modifiers. Especiallypreferred oil additives comprise alkyl esters of C₈-C₂₂ fatty acids,especially the methyl derivatives of C₁₂-C₁₈ fatty acids, for examplethe methyl esters of lauric acid, palmitic acid and oleic acid, beingimportant. Those esters are known as methyl laurate (CAS-111-82-0),methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). Apreferred fatty acid methyl ester derivative is Emery® 2230 and 2231(Cognis GmbH). Those and other oil derivatives are also known from theCompendium of Herbicide Adjuvants, 5th Edition, Southern IllinoisUniversity, 2000. Another preferred adjuvant is Adigor® (Syngenta AG)which is a methylated rapeseed oil-based adjuvant.

The application and action of the oil additives can be further improvedby combining them with surface-active substances, such as non-ionic,anionic or cationic surfactants. Examples of suitable anionic, non-ionicand cationic surfactants are listed on pages 7 and 8 of WO 97/34485.Preferred surface-active substances are anionic surfactants of thedodecylbenzylsulfonate type, especially the calcium salts thereof, andalso non-ionic surfactants of the fatty alcohol ethoxylate type. Specialpreference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having adegree of ethoxylation of from 5 to 40. Examples of commerciallyavailable surfactants are the Genapol types (Clariant AG). Alsopreferred are silicone surfactants, especially polyalkyl-oxide-modifiedheptamethyltrisiloxanes, which are commercially available e.g. as SilwetL-77®, and also perfluorinated surfactants. The concentration ofsurface-active substances in relation to the total additive is generallyfrom 1 to 30% by weight. Examples of oil additives that consist ofmixtures of oils or mineral oils or derivatives thereof with surfactantsare Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and Actipron® (BP OilUK Limited, GB).

The said surface-active substances may also be used in the formulationsalone, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oiladditive/surfactant mixture can contribute to a further enhancement ofaction. Suitable solvents are, for example, Solvesso® (ESSO) andAromatic Solvent® (Exxon Corporation). The concentration of suchsolvents can be from 10 to 80% by weight of the total weight. Such oiladditives, which may be in admixture with solvents, are described, forexample, in U.S. Pat. No. 4,834,908. A commercially available oiladditive disclosed therein is known by the name MERGE® (BASFCorporation). A further oil additive that is preferred according to theinvention is SCORE® (Syngenta Crop Protection Canada.)

In addition to the oil additives listed above, in order to enhance theactivity of the compositions according to the invention it is alsopossible for formulations of alkylpyrrolidones, (e.g. Agrimax®) to beadded to the spray mixture. Formulations of synthetic lattices, such as,for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene(e.g. Bond®, Courier® or Emerald®) can also be used. Solutions thatcontain propionic acid, for example Eurogkem Pen-e-trate®, can also bemixed into the spray mixture as activity-enhancing agents.

The herbicidal formulations generally contain from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, of a compound of formula I andfrom 1 to 99.9% by weight of a formulation adjuvant, which preferablyincludes from 0 to 25% by weight of a surface-active substance. Whereascommercial products will preferably be formulated as concentrates, theend user will normally employ dilute formulations.

The rate of application of the compounds of formula I may vary withinwide limits and depends upon the nature of the soil, the method ofapplication (pre- or post-emergence; seed dressing; application to theseed furrow; no tillage application etc.), the crop plant, the weed orgrass to be controlled, the prevailing climatic conditions, and otherfactors governed by the method of application, the time of applicationand the target crop. The compounds of formula I according to theinvention are generally applied at a rate of 1 to 4000 g/ha, especiallyfrom 5 to 1000 g/ha. Preferred formulations have especially thefollowing compositions:

(%=percent by weight):

Emulsifiable Concentrates:

-   active ingredient: 1 to 95%, preferably 60 to 90%-   surface-active agent: 1 to 30%, preferably 5 to 20%-   liquid carrier: 1 to 80%, preferably 1 to 35%    Dusts:-   active ingredient: 0.1 to 10%, preferably 0.1 to 5%-   solid carrier: 99.9 to 90%, preferably 99.9 to 99%    Suspension Concentrates:-   active ingredient: 5 to 75%, preferably 10 to 50%-   water: 94 to 24%, preferably 88 to 30%-   surface-active agent: 1 to 40%, preferably 2 to 30%    Wettable Powders:-   active ingredient: 0.5 to 90%, preferably 1 to 80%-   surface-active agent: 0.5 to 20%, preferably 1 to 15%-   solid carrier: 5 to 95%, preferably 15 to 90%    Granules:-   active ingredient: 0.1 to 30%, preferably 0.1 to 15%-   solid carrier: 99.5 to 70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, theinvention.

F1. Emulsifiable concentrates a) b) c) d) active ingredient 5% 10% 25%50% calcium dodecylbenzene- 6%  8%  6%  8% sulfonate castor oilpolyglycol ether 4% —  4%  4% (36 mol of ethylene oxide) octylphenolpolyglycol ether —  4% —  2% (7-8 mol of ethylene oxide) NMP — — 10% 20%arom. hydrocarbon 85%  78% 55% 16% mixture C₉-C₁₂

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient  5% 10% 50% 90%1-methoxy-3-(3-methoxy- — 20% 20% — propoxy)-propane polyethylene glycolMW 400 20% 10% — — NMP — — 30% 10% arom. hydrocarbon 75% 60% — — mixtureC₉-C₁₂

The solutions are suitable for application in the form of microdrops.

F3. Wettable powders a) b) c) d) active ingredient 5% 25%  50%  80%sodium lignosulfonate 4% — 3% — sodium lauryl sulfate 2% 3% —  4% sodiumdiisobutylnaphthalene- — 6% 5%  6% sulfonate octylphenol polyglycolether — 1% 2% — (7-8 mol of ethylene oxide) highly dispersed silicicacid 1% 3% 5% 10% kaolin 88%  62%  35%  —

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, yielding wettablepowders which can be diluted with water to give suspensions of anydesired concentration.

F4. Coated granules a) b) c) active ingredient 0.1% 5% 15% highlydisperse silicic acid 0.9% 2%  2% inorg. carrier (diameter 99.0% 93% 83% 0.1-1 mm) e.g. CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride, the solutionis sprayed onto the carrier and the solvent is subsequently evaporatedoff in vacuo.

F5. Coated granules a) b) c) active ingredient 0.1% 5% 15% polyethyleneglycol MW 200 1.0% 2%  3% highly disperse silicic acid 0.9% 1%  2%inorg. carrier (diameter 98.0% 92%  80% 0.1-1 mm) e.g. CaCO₃ or SiO₂

The finely ground active ingredient is applied uniformly, in a mixer, tothe carrier moistened with polyethylene glycol. Non-dusty coatedgranules are obtained in this manner.

F6. Extruded granules a) b) c) d) active ingredient 0.1% 3% 5% 15%sodium lignosulfonate 1.5% 2% 3%  4% carboxymethylcellulose 1.4% 2% 2% 2% kaolin 97.0% 93%  90%  79%

The active ingredient is mixed and ground with the adjuvants and themixture is moistened with water. The resulting mixture is extruded andthen dried in a stream of air.

F7. Dusts a) b) c) active ingredient 0.1%  1%  5% talcum 39.9% 49% 35%kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with thecarriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient 3% 10%  25% 50%  ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether — 1% 2% —(15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5%carboxymethylcellulose 1% 1% 1% 1% 37% aqueous formaldehyde 0.2%  0.2%   0.2%   0.2%   solution silicone oil emulsion 0.8%   0.8%   0.8%  0.8%   water 87%  79%  62%  38% 

The finely ground active ingredient is intimately mixed with theadjuvants, yielding a suspension concentrate from which suspensions ofany desired concentration can be prepared by dilution with water.

The invention relates also to a method for the selective control ofgrasses and weeds in crops of useful plants, which comprises treatingthe useful plants or the area under cultivation or the locus thereofwith a compound of formula I.

Crops of useful plants in which the compositions according to theinvention can be used include especially cereals, cotton, soybeans,sugar beet, sugar cane, plantation crops, rape, maize and rice, and fornon-selective weed control. The term “crops” is to be understood as alsoincluding crops that have been rendered tolerant to herbicides orclasses of herbicides (for example ALS, GS, EPSPS, PPO, ACCase and HPPDinhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant e.g.to imidazolinones, such as imazamox, by conventional methods of breedingis Clearfield® summer rape (Canola). Examples of crops that have beenrendered tolerant to herbicides by genetic engineering methods includee.g. glyphosate- and glufosinate-resistant maize varieties commerciallyavailable under the trade names RoundupReady® and LibertyLink®. Theweeds to be controlled may be both monocotyledonous and dicotyledonousweeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria,Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus,Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia,Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea,Chrysanthemum, Galium, Viola and Veronica.

Crops are also to be understood as being those which have been renderedresistant to harmful insects by genetic engineering methods, for exampleBt maize (resistant to European corn borer), Bt cotton (resistant tocotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).Examples of Bt maize are the Bt-176 maize hybrids of NK® (SyngentaSeeds). The Bt toxin is a protein that is formed naturally by Bacillusthuringiensis soil bacteria. Examples of toxins and transgenic plantsable to synthesise such toxins are described in EP-A-451 878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examplesof transgenic plants that contain one or more genes which code for aninsecticidal resistance and express one or more toxins are KnockOut®(maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton),NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops and theirseed material can be resistant to herbicides and at the same time alsoto insect feeding (“stacked” transgenic events). Seed can, for example,have the ability to express an insecticidally active Cry3 protein and atthe same time be glyphosate-tolerant. The term “crops” is to beunderstood as also including crops obtained as a result of conventionalmethods of breeding or genetic engineering which contain so-calledoutput traits (e.g. improved flavour, storage stability, nutritionalcontent).

Areas under cultivation are to be understood as including land where thecrop plants are already growing as well as land intended for thecultivation of those crop plants.

The compounds of formula I according to the invention can also be usedin combination with other herbicides. The following mixtures of thecompound of formula I are especially important. Preferably, in thesemixtures, the compound of the formula I is one of those compounds listedin Tables 1 to 204 below:

compound of formula I+acetochlor, compound of formula I+acifluorfen,compound of formula I+acifluorfen-sodium, compound of formulaI+aclonifen, compound of formula I+acrolein, compound of formulaI+alachlor, compound of formula I+alloxydim, compound of formula I+allylalcohol, compound of formula I+ametryn, compound of formulaI+amicarbazone, compound of formula I+amidosulfuron, compound of formulaI+aminopyralid, compound of formula I+amitrole, compound of formulaI+ammonium sulfamate, compound of formula I+anilofos, compound offormula I+asulam, compound of formula I+atrazine, formula I+aviglycine,formula I+azafenidin, compound of formula I+azimsulfuron, compound offormula I+BCPC, compound of formula I+beflubutamid, compound of formulaI+benazolin, formula I+bencarbazone, compound of formula I+benfluralin,compound of formula I+benfuresate, compound of formula I+bensulfuron,compound of formula I+bensulfuron-methyl, compound of formulaI+bensulide, compound of formula I+bentazone, compound of formulaI+benzfendizone, compound of formula I+benzobicyclon, compound offormula I+benzofenap, compound of formula I+bifenox, compound of formulaI+bilanafos, compound of formula I+bispyribac, compound of formulaI+bispyribac-sodium, compound of formula I+borax, compound of formulaI+bromacil, compound of formula I+bromobutide, formula I+bromophenoxim,compound of formula I+bromoxynil, compound of formula I+butachlor,compound of formula I+butafenacil, compound of formula I+butamifos,compound of formula I+butralin, compound of formula I+butroxydim,compound of formula I+butylate, compound of formula I+cacodylic acid,compound of formula I+calcium chlorate, compound of formulaI+cafenstrole, compound of formula I+carbetamide, compound of formulaI+carfentrazone, compound of formula I+carfentrazone-ethyl, compound offormula I+CDEA, compound of formula I+CEPC, compound of formulaI+chlorflurenol, compound of formula I+chlorflurenol-methyl, compound offormula I+chloridazon, compound of formula I+chlorimuron, compound offormula I+chlorimuron-ethyl, compound of formula I+chloroacetic acid,compound of formula I+chlorotoluron, compound of formula I+chlorpropham,compound of formula I+chlorsulfuron, compound of formula I+chlorthal,compound of formula I+chlorthal-dimethyl, compound of formulaI+cinidon-ethyl, compound of formula I+cinmethylin, compound of formulaI+cinosulfuron, compound of formula I+cisanilide, compound of formulaI+clethodim, compound of formula I+clodinafop, compound of formulaI+clodinafop-propargyl, compound of formula I+clomazone, compound offormula I+clomeprop, compound of formula I+clopyralid, compound offormula I+cloransulam, compound of formula I+cloransulam-methyl,compound of formula I+CMA, compound of formula I+4-CPB, compound offormula I+CPMF, compound of formula I+4-CPP, compound of formula I+CPPC,compound of formula I+cresol, compound of formula I+cumyluron, compoundof formula I+cyanamide, compound of formula I+cyanazine, compound offormula I+cycloate, compound of formula I+cyclosulfamuron, compound offormula I+cycloxydim, compound of formula I+cyhalofop, compound offormula I+cyhalofop-butyl, compound of formula I+2,4-D, compound offormula I+3,4-DA, compound of formula I+daimuron, compound of formulaI+dalapon, compound of formula I+dazomet, compound of formula I+2,4-DB,compound of formula I+3,4-DB, compound of formula I+2,4-DEB, compound offormula I+desmedipham, formula I+desmetryn, compound of formulaI+dicamba, compound of formula I+dichlobenil, compound of formulaI+ortho-dichlorobenzene, compound of formula I+para-dichlorobenzene,compound of formula I+dichlorprop, compound of formula I+dichlorprop-P,compound of formula I+diclofop, compound of formula I+diclofop-methyl,compound of formula I+diclosulam, compound of formula I+difenzoquat,compound of formula I+difenzoquat metilsulfate, compound of formulaI+diflufenican, compound of formula I+diflufenzopyr, compound of formulaI+dimefuron, compound of formula I+dimepiperate, compound of formulaI+dimethachlor, compound of formula I+dimethametryn, compound of formulaI+dimethenamid, compound of formula I+dimethenamid-P, compound offormula I+dimethipin, compound of formula I+dimethylarsinic acid,compound of formula I+dinitramine, compound of formula I+dinoterb,compound of formula I+diphenamid, formula I+dipropetryn, compound offormula I+diquat, compound of formula I+diquat dibromide, compound offormula I+dithiopyr, compound of formula I+diuron, compound of formulaI+DNOC, compound of formula I+3,4-DP, compound of formula I+DSMA,compound of formula I+EBEP, compound of formula I+endothal, compound offormula I+EPTC, compound of formula I+esprocarb, compound of formulaI+ethalfluralin, compound of formula I+ethametsulfuron, compound offormula I+ethametsulfuron-methyl, formula I+ethephon, compound offormula I+ethofumesate, compound of formula I+ethoxyfen, compound offormula I+ethoxysulfuron, compound of formula I+etobenzanid, compound offormula I+fenoxaprop-P, compound of formula I+fenoxaprop-P-ethyl,compound of formula I+fentrazamide, compound of formula I+ferroussulfate, compound of formula I+flamprop-M, compound of formulaI+flazasulfuron, compound of formula I+florasulam, compound of formulaI+fluazifop, compound of formula I+fluazifop-butyl, compound of formulaI+fluazifop-P, compound of formula I+fluazifop-P-butyl, formulaI+fluazolate, compound of formula I+flucarbazone, compound of formulaI+flucarbazone-sodium, compound of formula I+flucetosulfuron, compoundof formula I+fluchloralin, compound of formula I+flufenacet, compound offormula I+flufenpyr, compound of formula I+flufenpyr-ethyl, formulaI+flumetralin, compound of formula I+flumetsulam, compound of formulaI+flumiclorac, compound of formula I+flumiclorac-pentyl, compound offormula I+flumioxazin, formula I+flumipropin, compound of formulaI+fluometuron, compound of formula I+fluoroglycofen, compound of formulaI+fluoroglycofen-ethyl, formula I+fluoxaprop, formula I+flupoxam,formula I+flupropacil, compound of formula I+flupropanate, compound offormula I+flupyrsulfuron, compound of formulaI+flupyrsulfuron-methyl-sodium, compound of formula I+flurenol, compoundof formula I+fluridone, compound of formula I+fluorochloridone, compoundof formula I+fluoroxypyr, compound of formula I+flurtamone, compound offormula I+fluthiacet, compound of formula I+fluthiacet-methyl, compoundof formula I+fomesafen, compound of formula I+foramsulfuron, compound offormula I+fosamine, compound of formula I+glufosinate, compound offormula I+glufosinate-ammonium, compound of formula I+glyphosate,compound of formula I+halosulfuron, compound of formulaI+halosulfuron-methyl, compound of formula I+haloxyfop, compound offormula I+haloxyfop-P, compound of formula I+HC-252, compound of formulaI+hexazinone, compound of formula I+imazamethabenz, compound of formulaI+imazamethabenz-methyl, compound of formula I+imazamox, compound offormula I+imazapic, compound of formula I+imazapyr, compound of formulaI+imazaquin, compound of formula I+imazethapyr, compound of formulaI+imazosulfuron, compound of formula I+indanofan, compound of formulaI+iodomethane, compound of formula I+iodosulfuron, compound of formulaI+iodosulfuron-methyl-sodium, compound of formula I+ioxynil, compound offormula I+isoproturon, compound of formula I+isouron, compound offormula I+isoxaben, compound of formula I+isoxachlortole, compound offormula I+isoxaflutole, formula I+isoxapyrifop, compound of formulaI+karbutilate, compound of formula I+lactofen, compound of formulaI+lenacil, compound of formula I+linuron, compound of formula I+MAA,compound of formula I+MAMA, compound of formula I+MCPA, compound offormula I+MCPA-thioethyl, compound of formula I+MCPB, compound offormula I+mecoprop, compound of formula I+mecoprop-P, compound offormula I+mefenacet, compound of formula I+mefluidide, compound offormula I+mesosulfuron, compound of formula I+mesosulfuron-methyl,compound of formula I+mesotrione, compound of formula I+metam, compoundof formula I+metamifop, compound of formula I+metamitron, compound offormula I+metazachlor, compound of formula I+methabenzthiazuron, formulaI+methazole, compound of formula I+methylarsonic acid, compound offormula I+methyldymron, compound of formula I+methyl isothiocyanate,compound of formula I+metobenzuron, formula I+metobromuron, compound offormula I+metolachlor, compound of formula I+S-metolachlor, compound offormula I+metosulam, compound of formula I+metoxuron, compound offormula I+metribuzin, compound of formula I+metsulfuron, compound offormula I+metsulfuron-methyl, compound of formula I+MK-616, compound offormula I+molinate, compound of formula I+monolinuron, compound offormula I+MSMA, compound of formula I+naproanilide, compound of formulaI+napropamide, compound of formula I+naptalam, formula I+NDA-402989,compound of formula I+neburon, compound of formula I+nicosulfuron,formula I+nipyraclofen, formula I+n-methyl glyphosate, compound offormula I+nonanoic acid, compound of formula I+norflurazon, compound offormula I+oleic acid (fatty acids), compound of formula I+orbencarb,compound of formula I+orthosulfamuron, compound of formula I+oryzalin,compound of formula I+oxadiargyl, compound of formula I+oxadiazon,compound of formula I+oxasulfuron, compound of formula I+oxaziclomefone,compound of formula I+oxyfluorfen, compound of formula I+paraquat,compound of formula I+paraquat dichloride, compound of formulaI+pebulate, compound of formula I+pendimethalin, compound of formulaI+penoxsulam, compound of formula I+pentachlorophenol, compound offormula I+pentanochlor, compound of formula I+pentoxazone, compound offormula I+pethoxamid, compound of formula I+petrolium oils, compound offormula I+phenmedipham, compound of formula I+phenmedipham-ethyl,compound of formula I+picloram, compound of formula I+picolinafen,compound of formula I+pinoxaden, compound of formula I+piperophos,compound of formula I+potassium arsenite, compound of formulaI+potassium azide, compound of formula I+pretilachlor, compound offormula I+primisulfuron, compound of formula I+primisulfuron-methyl,compound of formula I+prodiamine, compound of formula I+profluazol,compound of formula I+profoxydim, formula I+prohexadione-calcium,compound of formula I+prometon, compound of formula I+prometryn,compound of formula I+propachlor, compound of formula I+propanil,compound of formula I+propaquizafop, compound of formula I+propazine,compound of formula I+propham, compound of formula I+propisochlor,compound of formula I+propoxycarbazone, compound of formulaI+propoxycarbazone-sodium, compound of formula I+propyzamide, compoundof formula I+prosulfocarb, compound of formula I+prosulfuron, compoundof formula I+pyraclonil, compound of formula I+pyraflufen, compound offormula I+pyraflufen-ethyl, formula I+pyrasulfotole, compound of formulaI+pyrazolynate, compound of formula I+pyrazosulfuron, compound offormula I+pyrazosulfuron-ethyl, compound of formula I+pyrazoxyfen,compound of formula I+pyribenzoxim, compound of formula I+pyributicarb,compound of formula I+pyridafol, compound of formula I+pyridate,compound of formula I+pyriftalid, compound of formula I+pyriminobac,compound of formula I+pyriminobac-methyl, compound of formulaI+pyrimisulfan, compound of formula I+pyrithiobac, compound of formulaI+pyrithiobac-sodium, formula I+pyroxasulfone (KIH-485), formulaI+pyroxulam, compound of formula I+quinclorac, compound of formulaI+quinmerac, compound of formula I+quinoclamine, compound of formulaI+quizalofop, compound of formula I+quizalofop-P, compound of formulaI+rimsulfuron, compound of formula I+sethoxydim, compound of formulaI+siduron, compound of formula I+simazine, compound of formulaI+simetryn, compound of formula I+SMA, compound of formula I+sodiumarsenite, compound of formula I+sodium azide, compound of formulaI+sodium chlorate, compound of formula I+sulcotrione, compound offormula I+sulfentrazone, compound of formula I+sulfometuron, compound offormula I+sulfometuron-methyl, compound of formula I+sulfosate, compoundof formula I+sulfosulfuron, compound of formula I+sulfuric acid,compound of formula I+tar oils, compound of formula I+2,3,6-TBA,compound of formula I+TCA, compound of formula I+TCA-sodium, formulaI+tebutam, compound of formula I+tebuthiuron, formula I+tefuryltrione,compound of formula I+tembotrione, compound of formula I+tepraloxydim,compound of formula I+terbacil, compound of formula I+terbumeton,compound of formula I+terbuthylazine, compound of formula I+terbutryn,compound of formula I+thenylchlor, compound of formula I+thiazafluoron,compound of formula I+thiazopyr, compound of formula I+thifensulfuron,compound of formula I+thiencarbazone, compound of formulaI+thifensulfuron-methyl, compound of formula I+thiobencarb, compound offormula I+tiocarbazil, compound of formula I+topramezone, compound offormula I+tralkoxydim, compound of formula I+tri-allate, compound offormula I+triasulfuron, compound of formula I+triaziflam, compound offormula I+tribenuron, compound of formula I+tribenuron-methyl, compoundof formula I+tricamba, compound of formula I+triclopyr, compound offormula I+trietazine, compound of formula I+trifloxysulfuron, compoundof formula I+trifloxysulfuron-sodium, compound of formula I+trifluralin,compound of formula I+triflusulfuron, compound of formulaI+triflusulfuron-methyl, compound of formula I+trihydroxytriazine,compound of formula I+trinexapac-ethyl, compound of formulaI+tritosulfuron, compound of formulaI+[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]aceticacid ethyl ester (CAS RN 353292-31-6), compound of formulaI+4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one(CAS RN 352010-68-5), and compound of formulaI+4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one.

The mixing partners of the compound of formula I may also be in the formof esters or salts, as mentioned e.g. in The Pesticide Manual, TwelfthEdition, British Crop Protection Council, 2000.

The mixing ratio of the compound of formula I to the mixing partner ispreferably from 1:100 to 1000:1.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of formula I with the mixing partner).

The compounds of formula I according to the invention can also be usedin combination with safeners. Preferably, in these mixtures, thecompound of the formula I is one of those compounds listed in Tables 1to 204 below. The following mixtures with safeners, especially, comeinto consideration:

compound of formula I+cloquintocet-mexyl, compound of formulaI+cloquintocet acid and salts thereof, compound of formulaI+fenchlorazole-ethyl, compound of formula I+fenchlorazole acid andsalts thereof, compound of formula I+mefenpyr-diethyl, compound offormula I+mefenpyr diacid, compound of formula I+isoxadifen-ethyl,compound of formula I+isoxadifen acid, compound of formula I+furilazole,compound of formula I+furilazole R isomer, compound of formulaI+benoxacor, compound of formula I+dichlormid, compound of formulaI+AD-67, compound of formula I+oxabetrinil, compound of formulaI+cyometrinil, compound of formula I+cyometrinil Z-isomer, compound offormula I+fenclorim, compound of formula I+cyprosulfamide, compound offormula I+naphthalic anhydride, compound of formula I+flurazole,compound of formula I+CL 304,415, compound of formula I+dicyclonon,compound of formula I+fluxofenim, compound of formula I+DKA-24, compoundof formula I+R-29148 and compound of formula I+PPG-1292. A safeningeffect can also be observed for the mixtures compound of the formulaI+dymron, compound of the formula I+MCPA, compound of the formulaI+mecopropand compound of the formula I+mecoprop-P.

The above-mentioned safeners and herbicides are described, for example,in the Pesticide Manual, Twelfth Edition, British Crop ProtectionCouncil, 2000. R-29148 is described, for example by P. B. Goldsbrough etal., Plant Physiology, (2002), Vol. 130 pp. 1497-1505 and referencestherein and PPG-1292 is known from WO09211761.

The rate of application of safener relative to the herbicide is largelydependent upon the mode of application. In the case of field treatment,generally from 0.001 to 5.0 kg of safener/ha, preferably from 0.001 to0.5 kg of safener/ha, and generally from 0.001 to 2 kg of herbicide/ha,but preferably from 0.005 to 1 kg/ha, are applied.

The herbicidal compositions according to the invention are suitable forall methods of application customary in agriculture, such as, forexample, pre-emergence application, post-emergence application and seeddressing. Depending upon the intended use, the safeners can be used forpretreating the seed material of the crop plant (dressing the seed orseedlings) or introduced into the soil before or after sowing, followedby the application of the (unsafened) compound of the formula I,optionally in combination with a co-herbicide. It can, however, also beapplied alone or together with the herbicide before or after emergenceof the plants. The treatment of the plants or the seed material with thesafener can therefore take place in principle independently of the timeof application of the herbicide. The treatment of the plant bysimultaneous application of herbicide and safener (e.g. in the form of atank mixture) is generally preferred. The rate of application of safenerrelative to herbicide is largely dependent upon the mode of application.In the case of field treatment, generally from 0.001 to 5.0 kg ofsafener/ha, preferably from 0.001 to 0.5 kg of safener/ha, are applied.In the case of seed dressing, generally from 0.001 to 10 g of safener/kgof seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied.When the safener is applied in liquid form, with seed soaking, shortlybefore sowing, it is advantageous to use safener solutions which containthe active ingredient in a concentration of from 1 to 10 000 ppm,preferably from 100 to 1000 ppm.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of formula I with the mixing partner).

The following examples illustrate the invention further but do not limitthe invention.

PREPARATION EXAMPLES Example 1 Preparation of3-[2-(4-chlorophenyl)-5-methylselenazol-4-yl]bicyclo[3.2.1]octane-2,4-dione

Step 1

Preparation of 2-(4-chlorophenyl)selenazole-5-carbaldehyde

To a suspension of 4-chloroselenobenzamide (219 mg, 1 mmol) and2-chloromalonaldehyde (160 mg, 1.5 mmol) in 1,2-dimethoxyethane (1.5 ml)is added magnesium carbonate (42 mg, 0.5 mmol) and the resulting mixtureis stirred at 60° C. under an atmosphere of nitrogen for 3 hours. Thecrude reaction mixture is then filtered through a plug of silica andwashed with ethyl acetate, and filtrate is concentrated to give a brownsolid. The crude product is purified by flash chromatography on silicagel to give 2-(4-chlorophenyl)selenazole-5-carbaldehyde (162 mg).

Step 2

Preparation of [2-(4-chlorophenyl)selenazol-5-yl]methanol

To a suspension of 2-(4-chlorophenyl)selenazole-5-carbaldehyde (130 mg,0.48 mmol) in methanol (5 ml) is added sodium borohydride (19 mg, 0.5mmol) at 0° C. The reaction mixture is stirred at 0° C. for 0.5 hour.The reaction mixture is quenched with saturated aqueous ammoniumchloride solution (10 ml), and extracted with dichloromethane (3×25 ml).The combined organic extracts are dried over anhydrous magnesiumsulfate, filtered and the filtrate is evaporated to dryness to give[2-(4-chlorophenyl)selenazol-5-yl]methanol (127 mg).

Step 3

Preparation of4-[2-(4-chlorophenyl)selenazol-5-ylmethoxy]bicyclo[3.2.1]oct-3-en-2-one

To a solution of [2-(4-chlorophenyl)selenazol-5-yl]methanol (300 mg, 1.1mmol) in dry tetrahydrofuran (5 ml) is added, in one portion, sodiumhydride (60% dispersion in mineral oil, 44 mg, 1.1 mmol). The reactionmixture is stirred for 5 minutes at room temperature and4-chlorobicyclo[3.2.1]oct-3-en-2-one (172 mg, 1.1 mmol) is added inone-portion. The reaction mixture is stirred at room temperatureovernight. Silica gel is added to the crude reaction mixture, thesolvent is evaporated under reduced pressure and the residue is purifiedby flash chromatography on silica gel to give4-[2-(4-chlorophenyl)selenazol-5-ylmethoxy]bicyclo[3.2.1]oct-3-en-2-one(275 mg).

Step 4

Preparation of3-[2-(4-chlorophenyl)-5-methylselenazol-4-yl]bicyclo[3.2.1]octane-2,4-dione

4-[2-(4-Chlorophenyl)selenazol-5-ylmethoxy]bicyclo[3.2.1]oct-3-en-2-one(260 mg, 0.66 mmol) is placed in a microwave vial and dissolved indiethylene glycol dimethyl ether (8 ml). 1-Butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide (0.1 ml) is added and the reactionmixture is heated at 210° C. for 30 minutes under microwave irradiation.Silica gel is added to the crude reaction mixture, the solvent isevaporated under reduced pressure and the residue is purified by flashchromatography on silica gel to give3-[2-(4-chlorophenyl)-5-methylselenazol-4-yl]bicyclo[3.2.1]octane-2,4-dione(108 mg).

Example 2 Preparation of3-[5-methyl-2-(4-trifluoromethoxyphenyl)thiazol-4-yl]bicyclo[3.2.1]octane-2,4-dione

Step 1

Preparation of4-(2-bromothiazol-5-ylmethoxy)bicyclo[3.2.1]oct-3-en-2-one

To a solution of (2-bromothiazol-5-yl)methanol (4.85 g, 25 mmol) and4-chloro-bicyclo[3.2.1]oct-3-en-2-one (3.92 g, 25 mmol) in anhydroustetrahydrofuran (100 ml) is added, in small portions, sodium hydride(60% dispersion in oil, 1.00 g, 25 mmol) at 0° C. The reaction mixtureis stirred overnight and allowed to warm to room temperature. Silica gelis added to the crude reaction mixture, the solvent is evaporated underreduced pressure and the residue is purified by flash chromatography onsilica gel to give4-(2-bromothiazol-5-ylmethoxy)bicyclo[3.2.1]oct-3-en-2-one (6.43 g)

Step 2

Preparation of3-[5-methyl-2-(4-trifluoromethoxyphenyl)thiazol-4-yl]-bicyclo[3.2.1]octane-2,4-dione

4-(2-Bromothiazol-5-ylmethoxy)bicyclo[3.2.1]oct-3-en-2-one (157, 0.5mmol), 4-trifluoromethoxyphenyl boronic acid (206 mg, 1 mmol), toluene(2 ml), caesium carbonate (183 mg, 0.6 mmol), and PEPPSI™ catalyst (51mg, 0.15 mmol) are mixed together in a microwave vial and heated to 150°C. for 30 minutes under microwave irradiation. The crude product isfiltered, and the filtrate is evaporated under reduced pressure. Theresidue is dissolved in diglyme (5 ml), 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide (0.1 ml) is added and the reactionmixture is heated at 230° C. for 30 minutes under microwave irradiation.Silica gel is added to the crude reaction mixture, the solvent isevaporated under reduced pressure and the residue is purified by flashchromatography on silica gel to give3-[5-methyl-2-(4-trifluoromethoxy-phenyl)thiazol-4-yl]bicyclo[3.2.1]octane-2,4-dione(84 mg)

Example 3 Preparation of4-[4-(2,4-dioxobicyclo[3.2.1]oct-3-yl)-5-methylthiophen-2-yl]benzoicacid

Step 1

Preparation of 4-(5-hydroxymethylthiophen-2-yl)benzoic acid methyl ester

Sodium borohydride (155 mg, 4.1 mmol) is added to a solution of4-(5-formylthiophen-2-yl)benzoic acid methyl ester (1.01 g, 4.1 mmol) inmethanol/dichloromethane (16 ml/4 ml) and the resulting solution isstirred for 90 minutes at room temperature. The reaction is quenched bythe addition of saturated aqueous ammonium chloride solution (100 ml)and extracted with dichloromethane (100 ml). The organic layer is washedwith brine, dried over magnesium sulphate, filtered and concentrated invacuo to give 4-(5-hydroxymethyl-thiophen-2-yl)benzoic acid methyl ester(800 mg)

Step 2

Preparation of4-[5-(4-oxobicyclo[3.2.1]oct-2-en-2-yloxymethyl)thiophen-2-yl]benzoicacid methyl ester

To a solution of 4-(5-hydroxymethylthiophen-2-yl)benzoic acid methylester (223 mg, 0.9 mmol) in dry tetrahydrofuran (5 ml) is added, in oneportion, sodium hydride (60% dispersion in mineral oil, 36 mg, 0.9mmol). The reaction mixture is stirred for 5 minutes at room temperatureand then 4-chlorobicyclo[3.2.1]oct-3-en-2-one (157 mg, 1.0 mmol) isadded in one portion. The reaction mixture is stirred at roomtemperature overnight. Silica gel is added to the crude reactionmixture, the solvent is evaporated under reduced pressure and theresidue is purified by flash chromatography on silica gel to give4-[(5-(4-oxo-bicyclo[3.2.1]oct-2-en-2-yloxymethyl)thiophen-2-yl]benzoicacid methyl ester (264 mg).

Step 3

Preparation of4-[4-(2,4-dioxobicyclo[3.2.1]oct-3-yl)-5-methylthiophen-2-yl]benzoicacid methyl ester

4-[5-(4-oxo-bicyclo[3.2.1]oct-2-en-2-yloxymethyl)thiophen-2-yl]benzoicacid methyl ester (264 mg, 0.71 mmol) is placed in a microwave vial anddissolved in diethylene glycol dimethyl ether (3 ml).1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (0.1 ml)is added and the reaction mixture is heated at 190° C. for 30 minutesunder microwave irradiation. Silica gel is added to the crude reactionmixture, the solvent is evaporated under reduced pressure and theresidue is purified by flash chromatography on silica gel to give4-[4-(2,4-dioxobicyclo[3.2.1]oct-3-yl)-5-methylthiophen-2-yl]benzoicacid methyl ester (213 mg).

Step 4

Preparation of4-[4-(2,4-dioxo-bicyclo[3.2.1]oct-3-yl)-5-methylthiophen-2-yl]benzoicacid

To a solution of4-[4-(2,4-dioxobicyclo[3.2.1]oct-3-yl)-5-methylthiophen-2-yl]benzoicacid methyl ester (60 mg, 0.16 mmol) in methanol (2 ml) is added 1Naqueous lithium hydroxide solution (2 ml) and the reaction stirred atroom temperature for 72 hours. The reaction is acidified with 2N aqueoushydrochloric acid (25 ml) and extracted with dichloromethane (25 ml).The organic layer is washed with brine, dried over magnesium sulphate,filtered and the filtrate is concentrated in vacuo to give4-[4-(2,4-dioxobicyclo[3.2.1]oct-3-yl)-5-methylthiophen-2-yl]benzoicacid (44 mg).

Example 4 Preparation of3-[2-(4-chlorophenyl)-5-ethylthiazol-4-yl]bicyclo[3.2.1]octane-2,4-dione

Step 1

Preparation of 1-[2-(4-chloro-phenyl)thiazol-5-yl]ethanol

To a suspension of 1-[2-(4-chlorophenyl)thiazol-5-yl]ethanone (5 g, 21mmol) in methanol (100 ml) is added sodium borohydride (832 mg, 22 mmol)at room temperature. The reaction mixture is stirred at room temperaturefor 1 hour. The reaction mixture is quenched with saturated aqueousammonium chloride solution (100 ml) and extracted with dichloromethane(2×150 ml). The combined organic extracts are dried over anhydrousmagnesium sulfate, filtered and evaporated to dryness to give1-[2-(4-chlorophenyl)thiazol-5-yl]ethanol (4.88 g).

Step 2

Preparation of4-{1-[2-(4-chlorophenyl)thiazol-5-yl]ethoxy}bicyclo[3.2.1]oct-3-en-2-one

To a solution of 1-[2-(4-chlorophenyl)thiazol-5-yl]ethanol (1.1 g, 4.6mmol) in anhydrous tetrahydrofuran (20 ml) is added, in one portion,sodium hydride (60% dispersion in mineral oil, 184 mg, 4.6 mmol). Thereaction mixture is stirred for 5 minutes at room temperature and4-chlorobicyclo[3.2.1]oct-3-en-2-one (720 mg, 4.6 mmol) is added in oneportion. The reaction mixture is stirred at room temperature overnight.Silica gel is added to the crude reaction mixture, the solvent isevaporated under reduced pressure and the residue is purified by flashchromatography on silica gel to give4-{1-[2-(4-chlorophenyl)thiazol-5-yl]ethoxy}bicyclo[3.2.1]oct-3-en-2-one(1.24 g)

Step 3

Preparation of3-[2-(4-chlorophenyl)-5-ethylthiazol-4-yl]bicyclo[3.2.1]octane-2,4-dione

4-{1-[2-(4-chlorophenyl)thiazol-5-yl]ethoxy}bicyclo[3.2.1]oct-3-en-2-one(1.25 g, 3.47 mmol) is placed in a microwave vial and dissolved indiethylene glycol dimethyl ether (15 ml). 1-Butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide (0.1 ml) is added and the reactionmixture is heated at 230° C. for 30 minutes under microwave irradiation.Silica gel is added to the crude reaction mixture, the solvent isevaporated under reduced pressure and the residue is purified by flashchromatography on silica gel to give3-[2-(4-chlorophenyl)-5-ethyl-thiazol-4-yl]bicyclo[3.2.1]octane-2,4-dione(660 mg).

Example 5 Preparation of3-(6-methyl-2-methylsulfanyl-pyrimidin-4-yl)-bicyclo[3.2.1]octane-2,4-dione

A microwave vial is charged with4-chloro-2-methyl-6-thiomethylpyrimidine (174 mg, 1 mmol),2,2,6,6-tetramethyl-pyran-3,5-dione (170 mg, 1 mmol), palladium acetate(12 mg, 0.05 mmol), X-Phos (48 mg, 0.1 mmol) and potassium phosphate(424 mg, 2 mmol). 1,2-dimethoxyethane (3 ml) is added and the reactionheated to 140° C., with stirring, for 30 minutes. Silica gel is added tothe crude reaction mixture, the solvent is evaporated under reducedpressure and the residue is purified by flash chromatography on silicagel to give4-[2-(4-Chloro-phenyl)-5-methyl-pyrimidin-4-yl]-2,2,6,6-tetramethyl-pyran-3,5-dione(191 mg).

Example 6 Preparation of3-[2-(4-chloro-phenyl)thiazol-4-yl]bicyclo[3.2.1]octane-2,4-dione

Step 1

Preparation of chloro-acetic acid 4-oxo-bicyclo[3.2.1]oct-2-en-2-ylester

Into a 250 ml round bottom flask containing thebicyclo[3.2.1]octane-2,4-dione (10 g, 72 mmol) is added drydichloromethane (100 ml) and pyridine (6.28 g, 87 mmol). To the stirredmixture is added dropwise over a period of 15 minutes the chloroacetylchloride (9.82 g, 72 mmol) diluted in dichloromethane (100 ml). Thereaction mixture is therefore stirred for 2 hours at room temperature.The reaction mixture is therefore poured into 100 ml of aqueous 2N HCland extracted with ethyl acetate (2×100 ml). The combined organicextracts are dried over magnesium sulphate, filtered and evaporatedunder reduced pressure to give an orange oil. The crude product isdistilled under reduced pressure to give chloro-acetic acid4-oxo-bicyclo[3.2.1]oct-2-en-2-yl ester (13.4 g).

Step 2

Preparation of 3-(2-chloro-acetyl)bicyclo[3.2.1]octane-2,4-dione

Into a 250 ml round bottom flask containing a suspension of anhydrousaluminium chloride (10 g, 75 mmol) in 1,2-dichloroethane (80 ml) isadded dropwise over 20 minutes chloro-acetic acid4-oxo-bicyclo[3.2.1]oct-2-en-2-yl ester (6 g, 28 mmol) diluted in1,2-dichloroethane (20 ml), The resultant reaction mixture is stirredovernight at room temperature. The reaction is therefore poured into amix of ice and aqueous 2N HCl (100 ml) and extracted withdichloromethane (3×50 ml). The combined organic layers are dried overmagnesium sulphate, filtered and evaporated under reduced pressure togive a crude mixture 3-(2-chloro-acetyl)bicyclo[3.2.1]octane-2,4-dione(4.2 g).

Step 3

Preparation of3-[2-(4-chloro-phenyl)thiazol-4-yl]bicyclo[3.2.1]octane-2,4-dione

3-(2-chloro-acetyl)bicyclo[3.2.1]octane-2,4-dione (3.16 g, 14.7 mmol)and 4-chloro-thiobenzamide (2.53 g, 14.7 mmol) are mixed together intoluene (50 ml) and heated under reflux overnight. Therefore, thereaction mixture was evaporated to a black gum and the gum was absorbedonto silica and purified by flash chromatography eluting with a gradientof hexane/ethyl acetate to give3-[2-(4-chloro-phenyl)thiazol-4-yl]bicyclo[3.2.1]octane-2,4-dione (2.6g).

Additional compounds in Table T1 below are prepared by similar methodsusing appropriate starting materials.

Where more than one tautomer or rotational conformer is observed in theproton NMR spectrum, the data shown below are for the mixture of isomersand conformers.

TABLE T1 Compound ¹H nmr (CDCl₃ unless stated) or Number Structure otherphysical data T1 

δ ppm 1.59 (m, 1H), 1.84 (m, 2H), 2.11-2.18 (m, 3H), 2.49 (t, 3H), 3.06(m, 2H), 7.39 (d, 2H), 7.69 (d, 2H) T2 

δ ppm 1.59 (m, 1H), 1.80-1.91 (m, 2H), 2.08-2.20 (m, 3H), 2.42 (s, 3H),3.01-3.08 (m, 2H), 7.07 (t, 1H), 7.38 (d, 1H), 7.43 (d, 1H) T3 

δ ppm 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.45 (s, 3H), 3.05 (m,2H), 7.23 (d, 1H), 7.28 (d, 1H), 7.89 (s, 1H) T4 

δ ppm 1.60 (m, 1H), 1.89 (m, 2H), 2.14 (m, 3H), 2.43 (s, 3H), 2.45 (s,3H), 3.06 (s, 2H), 7.39 (d, 1H), 7.57 (d, 1H), 7.67 (s, 1H) T5 

δ ppm 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.46 (s, 3H), 3.06 (s,2H), 7.28 (d, 2H), 7.84 (d, 2H) T6 

δ ppm 1.60 (m, 1H), 1.82 (m, 2H), 2.11-2.19 (m, 3H), 2.47 (s, 3H), 3.09(m, 2H), 7.52 (d, 1H), 7.60 (dd, 1H), 7.81 (d, 1H) T7 

δ ppm 1.61 (m, 1H), 1.86 (m, 2H), 2.11-2.19 (m, 3H), 2.46 (s, 3H), 3.06(m, 2H), 7.57 (d, 1H), 7.90 (dd, 1H), 8.09 (d, 1H) T8 

δ ppm 1.63 (m, 1H), 1.87 (m, 2H), 2.17-2.24 (m, 3H), 2.49 (s, 3H), 3.19(m, 2H), 7.42 (d, 1H), 7.47 (dd, 1H), 7.59 (d, 1H), 7.68 (d, 1H), 8.03(dd, 1H), 8.18 (d, 1H) T9 

δ ppm 1.60 (m, 1H), 1.79-1.92 (m, 2H), 2.06-2.23 (m, 3H), 2.45 (s, 3H),2.97-3.13 (m, 2H), 7.50 (d, 1H), 7.62 (dd, 1H), 7.89 (d, 1H) T10 

δ ppm 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.4 (s, 3H), 2.45 (s,3H), 3.05 (m, 2H), 7.23 (d, 2H), 7.58 (d, 2H), 7.8 (d, 1H) T11 

δ ppm 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.40 (s, 3H), 2.45 (s,3H), 3.05 (m, 2H), 7.23 (d, 2H), 7.68 (d, 2H) T12 

δ ppm 1.61 (m, 1H), 1.79-1.92 (m, 2H), 2.10-2.24 (m, 3H), 2.45 (s, 3H),3.03-3.11 (m, 2H), 7.41-7.49 (m, 1H), 7.53 (dd, 1H), 7.60 (dd, 1H) T13 

δ ppm 1.61 (m, 1H), 1.85 (m, 2H), 2.07-2.22 (m, 3H), 2.47 (s, 3H), 3.02-3.12 (m, 2H), 7.20-7.29 (m, 2H), 7.91-7.99 (m, 1H) T14 

δ ppm 1.64 (m, 1H), 1.87 (m, 2H), 2.14-2.21 (m, 3H), 2.52 (s, 3H), 2.58(s, 3H), 3.10 (m, 2H), 7.29 (dd, 1H), 7.35 (d, 1H), 7.61 (d, 1H) T15 

δ ppm 1.60 (m, 1H), 1.81-1.90 (m, 2H), 2.08-2.22 (m, 3H), 2.45 (s, 3H),3.02-3.14 (m, 2H), 7.53-7.62 (m, 2H), 7.65-7.73 (m, 2H) T16 

δ ppm 1.56-1.67 (m, 3H), 2.08- 2.23 (m, 3H), 2.47 (s, 3H), 3.03-3.13 (m,2H), 7.42 (dd, 1H), 8.06 (dd, 1H), 8.82 (dd, 1H) T17 

δ ppm 1.60 (m, 1H), 1.79-1.90 (m, 2H), 2.07-2.21 (m, 3H), 2.45 (s, 3H),3.02-3.11 (m, 2H), 7.41 (d, 2H), 7.75 (d, 2H) T18 

δ ppm 1.61(m, 1H), 1.84 (m, 2H), 2.12-2.19 (m, 3H), 2.42 (s, 3H), 3.11(m, 2H), 4.01 (s, 3H), 6.85 (d, 1H), 8.03 (dd, 1H), 8.64 (d, 1H) T19 

δ ppm 1.31 (t, 3H), 1.60 (m, 1H), 1.84 (m, 2H), 2.07-2.21 (m, 3H), 2.88(q, 2H), 3.06 (m, br, 2H), 7.41 (d, 2H), 7.76 (d, 2H) T20 

δ ppm 1.3 (t, 3H), 1.58 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.4 (s,3H), 2.88 (q, 2H), 3.05 (m, 2H), 7.38 (d, 1H), 7.58 (d, 1H), 7.7 (s, 1H)T21 

δ ppm 1.3 (t, 3H), 1.6 (m, 1H), 1.85 (m, 2H), 2.18 (m, 3H), 2.3 (s, 3H),2.4 (s, 3H), 2.84 (q, 2H), 3.10 (m, 2H), 7.1 (d, 2H) 7.20 (d, 1H), 7.30(d, 1H), 7.4 (d, 1H), 7.68 (d, 1H), 7.7 (s, 1H) T22 

δ ppm 1.3 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.88 (m,2H), 3.05 (m, 2H), 7.50 (d, 1H), 7.65 (d, 1H), 7.9 (s, 1H). T23 

(CD₃OD) 

 ppm 1.71 (m, 1H), 1.84 (d, 2H), 2.20 (s, 3H), 2.15-2.30 (m, 3H),2.98-3.07 (m, 2H), 7.01 (s, 1H), 7.35 (d, 2H), 7.55 (d, 2H) T24 

(CD₃OD) 

 ppm 1.70 (m, 1H), 1.85 (m, 2H), 2.23 (m, 6H) 3.03 (m, 2H), 7.16 (s,1H), 7.67 (d, 2H), 8.00 (d, 2H) T25 

δ ppm 1.40-1.70 (m, 8H), 2.31 (s, 3H), 3.92 (s, 3H), 7.15 (s, 1H), 7.59(d, 2H), 8.01 (d, 2H) T26 

δ ppm 1.32 (t, 3H), 1.61 (m, 1H), 1.80 (m, 2H), 2.14 (m, 3H), 2.92 (q,2H), 3.06 (m, 2H), 7.23 (m, 2H), 7.96 (t, 1H) T27 

δ ppm 1.31 (t, 3H), 1.60 (m, 1H), 1.81 (m, 2H), 2.16 (m, 3H), 2.89 (q,2H), 3.06 (m, 2H), 7.46 (m, 1H), 7.55 (m, 1H), 7.62 (dd, 1H) T28 

δ ppm 1.31 (t, 3H), 1.60 (m, 1H), 1.81 (m, 2H), 2.15 (m, 3H), 2.88 (q,2H), 3.06 (m, 2H), 7.57 (m, 2H) 7.69 (m, 2H) T29 

δ ppm 1.32 (t, 3H), 1.59 (dt, 1H), 1.83 (m, 2H), 2.14 (m, 3H), 2.97 (q,2H), 3.06 (m, 2H), 7.11 (m, 2H) T30 

δ ppm 1.60 (m, 1H), 1.84 (m, 2H), 2.15 (m, 3H), 2.45 (s, 3H), 3.05 (m,2H), 7.53 (d, 2H), 7.77 (d, 2H) T31 

δ ppm 1.70 (m, 1H), 1.8 (d, 2H), 2.1 (s, 3H), 2.20 (m, 3H), 3.00 (m,2H), 7.45 (d, 2H), 7.85 (m 2H) T32 

δ ppm 1.60 (m, 1H), 1.87 (m, 2H), 2.16 (m, 3H), 2.47 (s, 3H), 3.07 (m,2H), 7.39 (m, 1H), 7.42 (m, 1H), 7.88 (m, 1H) T33 

δ ppm 1.36 (t, 3H), 1.64 (m, 1H), 1.89 (m, 2H), 2.18 (m, 3H), 2.96 (q,2H), 3.11 (m, 2H), 7.42 (m, 1H), 7.45 (m, 1H), 7.93 (t, 1H) T34 

δ ppm 1.59 (dt, 1H), 1.83 (m, 2H), 2.13 (m, 3H), 2.41 (s, 3H), 3.04 (m,2H), 6.89 (d, 1H), 7.19 (d, 1H) T35 

δ ppm 1.61 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.46 (s, 3H), 3.05 (m,2H), 7.89 (m, 2H), 8.63 (s, 1H) T36 

δ ppm 1.28 (t, 3H), 1.58 (dt, 1H), 1.85 (m, 2H), 2.14 (m, 3H), 2.84 (m,2H), 3.05 (m, 2H), 6.89 (d, 1H), 7.20 (d, 1H) T37 

δ ppm 1.60 (m, 1H), 1.83 (m, 2H), 2.15 (m, 3H), 2.47 (s, 3H), 2.54 (s,3H), 3.09 (m, 2H), 7.40 (dd, 1H), 7.49 (m, 2H) T38 

δ ppm 1.32 (t, 3H), 1.59 (m, 1H), 1.84 (m, 2H), 2.13 (m, 3H), 2.54 (s,3H), 2.91 (q, 2H), 3.09 (m, 2H), 7.40 (dd, 1H), 7.50 (m, 2H) T39 

δ ppm 1.32 (t, 3H), 1.59 (m, 1H), 1.84 (m, 2H), 2.15 (m, 3H), 2.87 (q,2H), 3.06 (m, 2H), 7.89 (m, 2H), 8.64 (s, 1H) T40 

δ ppm 1.60 (m, 1H), 1.84 (m, 2H), 2.16 (m, 3H), 3.08 (m, 2H), 4.01 (q,2H), 7.60 (d, 2H), 7.72 (d, 2H) T41 

δ ppm 1.27 (t, 3H), 1.58 (dt, 1H), 1.81 (m, 2H), 2.12 (m, 3H), 2.84 (q,2H), 3.03 (m, 2H), 5.25 (s, 2H), 6.91 (m, 2H), 7.27 (m, 2H) T42 

δ ppm 1.60 (dt, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.45 (s, 3H), 3.06 (m,2H), 6.56 (t, 1H), 7.18 (m, 2H), 7.82 (m, 2H) T43 

δ ppm 1.60 (m, 1H), 1.8 (m, 2H), 2.15 (m, 3H), 3.05 (m, 2H), 7.42 (d2H), 7.80 (m, 2H), 8.3 (s, 1H), 14.4 (s, 1H) T44 

δ ppm 1.31 (t, 3H), 1.60 (dt, 1H), 1.85 (m, 2H), 2.14 (m, 3H), 2.89 (m,2H), 3.06 (m, 2H), 6.57 (t, 1H), 7.18 (m, 2H), 7.83 (m, 2H) T45 

δ ppm 1.31 (t, 3H), 1.57 (dt, 1H), 1.80 (m, 2H), 2.12 (m, 3H), 2.37 (s,3H), 2.91 (m, 2H), 3.03 (m, 2H), 7.05 (m, 1H), 7.10 (m, 1H) T46 

δ ppm 1.31 (t, 3H), 1.61 (dt, 1H), 1.81 (m, 2H), 2.15 (m, 3H), 2.85 (q,2H), 3.06 (m, 2H), 7.51 (d, 1H), 7.65 (dd, 1H), 7.92 (d, 1H) T47 

δ ppm 1.70 (m, 1H), 1.80 (d, 2H), 2.10 (s, 3H), 2.20 (m, 3H), 3.1 (m,2H), 7.18 (s, 1H), 7.20 (m, 1H), 7.95 (m, 1H) T48 

δ ppm 1.72 (m, 1H), 1.85 (d, 2H), 2.1 (s, 3H), 2.20 (m, 3H), 3.1 (m,2H), 7.20 (d, 1H), 7.20 (m, 1H), 7.95 (m, 1H) T49 

δ ppm 1.55 (m, 1H), 1.60 (m, 1H), 1.75 (m, 1H), 2.00 (m, 1H), 2.15 (m,2H), 3.05 (m, 2H), 7.40 (d, 2H), 7.70 (d, 2H), 11.0 (s, 1H) T50 

δ ppm 1.71 (m, 1H), 1.93 (m, 2H), 2.16 (m, 3H), 2.28 (d, 3H), 3.06 (m,2H), 5.77 (d, 1H), 7.16 (d, 1H) T51 

δ ppm 1.33 (t, 3H), 1.60 (m, 1H) 1.83 (m, 2H), 2.14 (m, 3H), 2.91 (q,2H), 3.06 (m, 2H), 7.38 (dd, 1H), 7.73 (m, 2H) T52 

δ ppm 1.56 (m, 1H), 1.79 (m, 2H), 2.11 (m, 3H), 2.44 (s, 3H), 3.03 (q,2H), 8.63 (s, 1H) T53 

δ ppm 1.33 (t, 3H), 1.61 (m, 1H), 1.97 (m, 2H), 2.14 (m, 3H), 2.91 (q,2H), 3.07 (m, 2H), 7.58 (d, 1H), 7.80 (d, 1H) T54 

δ ppm 1.30 (t, 3H), 1.50 (m, 1H), 1.80 (d, 2H), 2.10 (m 3H), 2.40 (s,3H), 2.90 (q, 2H), 3.00 (m, 2H), 7.20 (d, 2H), 7.70 (d, 2H) T55 

δ ppm 1.55 (m, 1H), 1.60 (m, 2H), 2.80 (m, 1H), 2.15 (m, 2H), 3.10 (m,2H), 7.45 (d, 2H), 7.70 (d, 2H), 11.2 (s, 1H) T56 

δ ppm 1.61 (m, 1H), 1.85 (m, 2H), 2.16 (m, 3H), 2.44 (s, 3H), 3.07 (m,2H), 7.44 (m, 3H), 7.82 (m, 2H) T57 

δ ppm 1.60 (m, 1H), 1.84 (m, 2H), 2.15 (m, 3H), 2.44 (s, 3H), 3.07 (m,2H), 7.13 (m, 2H), 7.80 (m, 2H) T58 

δ ppm 1.59 (m, 1H), 1.84 (m, 2H), 2.14 (m, 3H), 2.41 (s, 3H), 3.06 (m,2H), 6.95 (d, 2H), 7.75 (d, 2H) T59 

δ ppm 1.61 (m, 1H), 1.85 (m, 2H), 2.16 (m, 3H), 2.47 (s, 3H), 3.07 (m,2H), 7.69 (d, 2H), 7.92 (d, 2H) T60 

δ ppm 1.58 (m, 1H), 1.83 (m, 2H), 2.13 (m, 3H), 2.42 (s, 3H), 3.05 (m,2H), 7.39 (m, 1H), 7.45 (m, 1H), 7.76 (m, 1H) T61 

δ ppm 1.01 (d, 6H), 1.57 (m, 1H), 1.81 (m, 2H), 2.04-2.13 (m, 4H), 2.33(s, 3H), 2.92 (d, 2H), 3.07 (m, 2H), 6.93 (s (br), 1H) T62 

δ ppm 1.61 (m, 1H), 1.86 (m, 2H), 2.16 (m, 3H), 2.52 (s, 3H), 3.08 (m,2H), 7.29 (m, 1H), 7.56 (m, 1H), 7.81 (m, 1H) T63 

δ ppm 1.62 (m, 1H), 1.87 (m, 2H), 2.15 (m, 3H), 2.48 (s, 3H), 3.08 (m,2H), 6.40 (s (br), 1H), 7.53 (m, 2H), 7.83-7.92 (m, 4H), 8.28 (s, 1H)T64 

δ ppm 1.62 (m, 1H), 1.87 (m, 2H), 2.17 (m, 3H), 2.47 (s, 3H), 3.09 (m,2H), 4.34 (s, 4H), 6.94 (d, 1H) 7.36 (m, 2H) T65 

δ ppm 1.61 (m, 1H), 1.86 (m, 2H), 2.15 (m, 3H), 2.48 (s, 3H), 3.07 (m,2H), 7.72 (d, 2H), 7.92 (d, 2H) T66 

δ ppm 1.60 (m, 1H), 1.84 (m, 2H), 2.14 (m, 3H), 2.41 (s, 3H), 3.07 (m,2H), 3.49 (s, 3H), 5.22 (s, 2H), 7.09 (d, 2H), 7.74 (d, 2H) T67 

δ ppm 1.60 (m, 1H), 1.83 (m, 2H), 2.15 (m, 3H), 2.46 (s, 3H), 2.50 (s,3H), 2.65 (s, 3H), 3.06 (m, 2H) T68 

δ ppm 1.65 (m, 1H), 1.89 (m, 2H), 2.19 (m, 3H), 2.49 (s, 3H), 3.10 (m,2H), 3.97 (s, 3H), 6.84 (m, 1H), 7.76 (m, 1H) T69 

δ ppm 1.61 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.48 (s, 3H), 2.64 (s,3H), 3.07 (m, 2H), 7.90 (d, 2H), 8.02 (d, 2H) T70 

δ ppm 1.60 (m, 1H), 1.84 (m, 2H), 2.15 (m, 3H), 2.47 (s, 3H), 3.06 (m,2H), 6.97 (m, 2H), 7.99 (m, 1H) T71 

δ ppm 1.60 (m, 1H), 1.83 (m, 2H), 2.15 (m, 3H), 2.49 (s, 3H), 3.05 (m,2H), 7.35 (m, 2H), 7.50 (m, 1H), 7.89 (m, 1H) T72 

δ ppm 1.61 (m, 1H), 1.85 (m, 2H), 2.16 (m, 3H), 2.48 (s, 3H), 3.06 (m,2H), 3.95 (s, 3H), 7.88 (d, 2H), 8.10 (d, 2H) T73 

δ ppm 1.61 (m, 1H), 1.86 (m, 2H), 2.15 (m, 3H), 2.49 (s, 3H), 3.07 (m,2H), 7.31 (dd, 1H), 7.43 (d, 1H), 7.92 (d, 1H) T74 

δ ppm 1.62 (m, 1H), 1.85 (m, 2H), 2.16 (m, 3H), 2.46 (s, 3H), 3.07 (m,2H), 7.59 (d, 1H), 7.96 (dd, 1H), 8.11 (d, 1H) T75 

δ ppm 1.62 (m, 1H), 1.83 (m, 2H), 2.15 (m, 3H), 2.48 (s, 3H), 2.56 (s,3H), 3.07 (m, 2H), 7.30 (s, 1H), 8.60 (s, 1H) T76 

δ ppm 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.42 (s, 3H), 3.07 (m,2H), 3.94 (s, 3H), 7.00 (t, 1H), 7.54 (m, 2H) T77 

δ ppm 1.48 (t, 3H), 1.60 (m, 1H), 1.84 (m, 2H), 2.14 (m, 3H), 2.43 (s,3H), 3.05 (m, 2H), 4.16 (q, 3H), 6.98 (t, 1H), 7.53 (m, 2H) T78 

δ ppm 1.60 (m, 1H), 1.84 (m, 2H), 2.14 (m, 3H), 2.45 (s, 3H), 3.06 (m,2H), 5.35 (d, 1H), 5.83 (d, 1H), 6.74 (dd, 1H), 7.47 (d, 2H), 7.78 (d,2H) T79 

δ ppm 1.41 (d, 6H), 1.61 (m, 1H), 1.86 (m, 2H), 2.14 (m, 3H), 2.43 (s,3H), 3.09 (m, 2H), 4.63 (sept, 1H), 6.97 (d, 1H), 7.63 (dd, 1H) 7.82 (d,1H) T80 

δ ppm 0.30 (s, 9H), 1.61 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.46 (s,3H), 3.06 (m, 2H), 7.60 (d, 2H), 7.77 (d, 2H) T81 

δ ppm 1.59 (m, 1H), 1.85 (m, 2H), 2.14 (m, 3H), 2.45 (s, 3H), 2.52 (s,3H), 3.05 (m, 2H), 7.27 (m, 2H), 7.72 (m, 2H) T82 

δ ppm 1.62 (m, 1H), 1.86 (m, 2H), 2.14 (m, 3H), 2.48 (s, 3H), 2.77 (s,3H), 3.08 (m, 2H), 7.72 (m, 2H), 7.97 (m, 2H) T83 

δ ppm 1.30 (t, 3H), 1.59 (dt, 1H), 1.84 (m, 2H), 2.14 (m, 3H), 2.52 (s,3H), 2.88 (q, 2H), 3.06 (m, 2H), 7.27 (m, 2H), 7.74 (m, 2H) T84 

δ ppm 1.60 (dt, 1H), 1.86 (m, 1H), 2.15 (m, 3H), 2.49 (s, 3H), 3.06-3.09(m, 2H), 6.57 (t, 1H), 7.14 (dd, 1H), 7.30 (d, 1H), 7.93 (d, 1H) T85 

δ ppm 1.66 (m, 1H), 1.89 (m, 2H), 2.19 (m, 3H), 3.09 (m, 2H), 7.84 (m,1H), 8.13 (m, 1H), 8.37 (m, 1H) T86 

δ ppm 1.61 (m, 1H), 1.90 (m, 2H), 2.17 (m, 3H), 2.37 (s, 3H), 3.07 (m,2H), 7.19 (m, 2H), 7.35 (m, 2H), 8.15 (m, 1H), 8.31 (m, 1H), 8.59 (m,1H) T87 

δ ppm 1.27 (d, 6H), 1.58 (m, 1H), 1.84 (m, 2H), 2.14 (m, 3H), 2.45 (s,3H), 2.95 (sept, 1H), 3.05 (q, 2H), 7.29 (d, 2H), 7.73 (d, 2H) T88 

δ ppm 1.66 (dt, 1H), 1.87 (m, 2H), 2.19 (m, 3H), 2.24 (s, 3H), 3.05 (m,2H), 7.51 (m, 2H), 8.20 (m, 2H), 8.57 (s, 1H) T89 

δ ppm 1.30 (t, 3H), 1.90 (m, 3H), 2.05 (m, 3H), 3.00 (q, 2H), 3.30 (m2H), 7.40 (d, 2H), 7.70 (d, 2H) T90 

δ ppm 1.57 (m, 1H), 1.82 (m, 2H), 2.10-2.30 (m, 3H), 2.94 (t, 1H), 3.30(s, 3H), 3.42 (t, 1H), 7.54 (d, 2H), 7.94 (d, 2H) T91 

δ ppm 1.90 (d, 2H), 2.20 (s, 3H), 3.00 (s, 2H), 3.56 (d, 2H), 3.63 (d,2H), 7.30 (d, 2H), 7.40 (d, 2H) T92 

δ ppm 1.60 (m, 1H), 1.89 (m, 1H), 2.15 (m, 3H), 2.47 (s, 3H), 3.06 (m,2H), 6.51 (t, 1H), 7.01 (m, 2H), 8.00 (t, 1H) T93 

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.9 (q,2H), 3.05 (m, 2H), 7.40 (m, 3H), 7.80 (m, 2H) T94 

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.89 (m, 2H), 2.20 (m, 3H), 2.90 (q,2H), 3.05 (m, 2H), 7.20 (m, 2H), 7.80 (m, 2H) T95 

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.90 (q,2H), 3.05 (m, 2H), 4.00 (s, 3H), 7.10 (m, 2H), 7.45 (m, 1H), 8.00 (m,1H) T96 

δ ppm 1.32 (t, 3H), 1.62 (m, 1H), 1.90 (m, 2H), 2.20 (m, 3H), 2.90 (q2H), 3.10 (m, 2H), 7.7 (d, 2H), 7.95 (d, 2H) T97 

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.90 (q,2H), 3.05 (m, 2H), 7.40 (m, 1H), 7.5 (m, 1H), 7.80 (m, 1H) T98 

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.90 (q,2H), 3.05 (m, 2H), 7.30 (m, 1H), 7.50 (m, 1H), 7.80 (m, 1H) T99 

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H) 2.90 (q,2H), 3.05 (m, 2H), 7.50 (m, 2H), 7.80 (m, 4H), 8.30 (s, 1H) T100

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.90 (q,2H), 3.05 (m, 2H), 4.30 (m, 4H), 6.90 (m, 1H), 7.30 (m, 2H) T101

δ ppm 1.40 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.20 (m, 3H), 2.90 (q2H), 3.05 (m, 2H), 7.80 (d, 2H), 8.00 (d, 2H) T102

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.20 (m, 3H), 2.90 (q,2H), 3.05 (m, 2H), 3.95 (s, 3H), 6.80 (m, 1H), 7.70 (m, 1H) T103

δ ppm 1.40 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.20 (m, 3H), 2.60 (s,3H), 2.90 (q, 2H), 3.05 (m, 2H), 7.90 (d, 2H), 8.10 (d, 2H) T104

δ ppm 1.35 (t, 3H), 1.60 (m, 1H), 1.90 (m, 2H), 2.20 (m, 3H), 2.90 (q,2H), 3.10 (m, 2H), 7.00 (m, 2H), 8.0 (m, 1H) T105

δ ppm 1.10 (m, 2H), 1.20 (d, 2H), 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m,2H), 2.20 (m, 3H), 2.40 (m, 1H), 2.80 (q, 2H), 3.05 (m, 2H) T106

δ ppm 1.40 (t, 3H), 1.60 (m, 1H), 1.80 (m, 2H), 2.20 (m, 3H), 2.90 (q,2H), 3.05 (m, 2H), 7.40 (m, 2H), 7.55 (m, 1H), 7.95 (m, 1H) T107

δ ppm 1.35 (t, 3H), 1.60 (m, 1H), 1.80 (m, 2H), 2.20 (m, 3H), 2.90 (q,2H), 3.05 (m, 2H), 4.00 (s, 3H), 7.90 (d, 2H), 8.10 (d, 2H) T108

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.20 (m, 3H), 2.90 (q,2H), 3.10 (m, 2H), 7.30 (d, 1H), 7.4 (d, 1H), 7.90 (d, 1H) T109

δ ppm 1.40 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.20 (m, 3H), 2.90 (q,2H), 3.05 (m, 2H), 7.60 (m, 1H), 7.90 (m, 1H), 8.10 (m, 1H) T110

δ ppm 1.40 (t, 3H), 1.60 (m, 1H), 1.80 (m, 2H), 2.20 (m, 3H), 2.70 (s3H), 2.90 (q, 2H), 3.05 (m, 2H), 7.30 (s, 1H), 8.60 (s, 1H) T111

δ ppm 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.85 (q,2H), 3.05 (m, 2H), 3.90 (s 3H), 7.00 (m, 1H), 7.6 (m, 2H) T112

δ ppm 1.35 (t, 3H), 1.50 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.20 (m,3H), 2.90 (q, 2H), 3.10 (m, 2H), 4.20 (q, 2H), 7.00 (t, 1H), 7.70 (m,2H) T113

δ ppm 1.35 (t, 3H), 1.65 (m, 1H) 1.80 (m, 2H), 2.20 (m, 3H), 2.90 (q,2H), 3.10 (m, 2H), 5.40 (d, 1H), 5.90 (d, 1H), 6.80 (m, 1H), 7.50 (d,2H), 7.80 (d, 2H) T114

δ ppm 1.30 (t, 3H), 1.40 (s, 6H), 1.60 (m, 1H), 1.85 (m, 2H), 2.10 (m,3H), 2.90 (q, 2H), 3.05 (m, 2H), 4.60 (m, 1H), 6.90 (d, 1H), 7.60 (d,1H), 7.80 (s, 1H) T115

δ ppm 0.30 (s, 9H), 1.30 (t, 3H), 1.60 (m, 1H), 1.85 (m, 2H), 2.10 (m,3H) 2.90 (q, 2H), 3.05 (m, 2H), 7.60 (d, 2H), 7.80 (d, 2H) T116

(CD₃OD) δ ppm 1.66 (dt, 1H), 1.76 (ddd, 2H), 2.13 (m, 3H), 2.45 (s, 3H),2.68 (s, 3H), 2.92 (dd, 2H), 8.34 (s, 1H) T117

δ ppm 1.63 (dt, 1H), 1.73 (m, 2H), 2.14 (m, 6H), 2.68 (s, 3H), 2.99 (dd,2H), 8.46 (s, 1H) T118

δ ppm 1.68 (dt, 1H), 1.89 (m, 2H), 2.20 (m, 3H), 2.79 (s, 3H), 3.11 (m,2H), 7.35 (d, 2H), 7.53 (d, 2H), 8.13 (d, 1H), 8.62 (s, 1H) T119

δ ppm 1.70 (m, 1H), 1.90 (m, 2H), 2.14 (m, 3H), 2.63 (s, 3H), 3.10 (m,2H), 7.37 (m, 2H), 7.80 (d, 1H), 8.68 (d, 1H) T120

δ ppm 1.15 (s, 3H), 1.55 (s, 3H), 2.30 (d, 1H), 2.55 (s, 3H), 2.72 (d,1H), 2.88 (m, 1H), 2.92 (m, 1H), 7.40 (d, 2H), 7.70 (d, 2H) T121

δ ppm 1.18 (s, 3H), 1.57 (s, 3H), 2.30 (d, 1H), 2.55 (s, 3H), 2.72 (d,1H), 2.88 (m, 1H), 2.92 (m, 1H), 7.58 (d, 2H), 7.68 (d, 2H)

Example 7 Preparation of 2,2-dimethylpropionic acid3-[2-(4-chloro-phenyl)-5-ethylthiazol-4-yl]-4-oxobicyclo[3.2.1]oct-2-en-2-ylester

To a solution of the3-[2-(4-chlorophenyl)-5-ethylthiazol-4-yl]bicyclo[3.2.1]octane-2,4-dione(100 mg, 0.28 mmol) in dichloromethane (5 ml) and triethylamine (140 μl,1 mmol) is added pivaloyl chloride (123 μl, 1 mmol) at room temperature.The reaction mixture is stirred overnight at room temperature. Silicagel is added to the crude reaction mixture, the solvent is evaporatedunder reduced pressure and the residue is purified by flashchromatography on silica gel to give 2,2-dimethylpropionic acid3-[2-(4-chlorophenyl)-5-ethylthiazol-4-yl]-4-oxobicyclo[3.2.1]oct-2-en-2-ylester (101 mg)

Additional compounds in Table P1 below are prepared by similar methodsusing appropriate starting materials.

Where more than one tautomer or rotational conformer is observed in theproton NMR spectrum, the data shown below are for the mixture of isomersand conformers.

TABLE P1 Compound ¹H nmr (CDCl₃ unless stated) or other Number Structurephysical data P1

δ ppm 0.81 (m, 3H), 0.94 (m, 1H), 1.25 (t, 3H), 1.56 (m, 1H), 1.73 (m,1H), 1.81 (m, 1H), 2.07 (m, 1H), 2.21 (m, 2H), 2.42 (d, 1H), 2.56 (m,2H), 3.15-3.08 (m, 2H), 7.35 (m, 2H), 7.81 (m, 2H) P2

δ ppm 1.02 (s, 9H), 1.24 (t, 3H), 1.73 (m, 1H), 1.82 (m, 1H), 2.07 (m,1H), 2.24 (m, 2H), 2.45 (m, 1H), 2.57 (q, 2H), 3.03 (m, 1H), 3.14 (m,1H), 7.36 (m, 2H), 7.77 (m, 2H) P3

δ ppm 1.05 (s, 9H), 1.60 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.45 (s,3H), 3.05 (m, 2H), 7.50 (d, 1H), 7.60 (d, 1H), 7.89 (s, 1H) P4

δ ppm 1.05 (s, 9H) , 1.72 (m,1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.30 (s,3H), 3.05 (m, 2H), 7.50 (d, 1H), 7.90 (d, 1H), 8.15 (s, 1H) P5

δ ppm 1.10 (t, 3H), 1.30 (t, 3H), 1.80 (dt, 1H), 1.91 (m, 1H), 2.07 (m,1H), 2.18-2.38 (m, 3H), 2.59 (q, 2H), 3.20 (m, 2H), 4.01 (m, 2H), 5.47(d, 1H), 7.36 (d, 1H), 7.40 (d, 2H), 7.83 (d, 2H) P6

δ ppm 1.74 (m, 1H), 1.82 (m, 1H), 2.01 (s, 3H), 2.08 (m, 1H), 2.15-2.30(m, 5H), 2.43 (d, 1H), 3.09 (t, 1H), 3.15 (t, 1H), 7.84 (dd, 1H), 7.98(d, 1H), 8.60 (d, 1H) P7

δ ppm 0.77-1.00 (m, 4H), 1.43 (m, 1H) 1.73 (dt, 1H), 1.82 (m, 1H), 2.08(m, 1H), 2.15-2.30 (m, 5H), 2.41 (d, 1H), 3.10 (t, 1H), 3.15 (t, 1H),7.84 (dd, 1H), 8.01 (d, 1H), 8.60 (d, 1H) P8

δ ppm 1.03 (m, 9H), 1.74 (m, 1H), 1.82 (m, 1H), 2.08 (m, 1H), 2.15-2.30(m, 5H), 2.43 (d, 1H), 3.09 (t, 1H), 3.15 (t, 1H), 7.84 (dd, 1H), 7.98(d, 1H), 8.60 (d, 1H) P9

δ ppm 1.33 (t, 3H), 1.63 (m, 1H), 1.86 2H), 2.17 (m, 2H), 2.45 (m, 1H),2.84 (q, 2H), 3.08 (m, 2H), 7.47 (d, 2H), 7.77 (d, 2H) P10

δ ppm 1.10 (s, 9H), 1.72 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.30 (s,3H), 3.05 (m, 2H), 7.40 (d, 2H), 7.80 (d, 2H) P11

δ ppm 1.30 (t, 3H), 1.72 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.30 (s,3H), 3.05 (m, 2H), 4.20 (q, 2H), 4.60 (s, 2H), 7.38 (d, 2H), 7.80 (d,2H) P12

δ ppm 1.72 (m, 1H), 1.81 (m, 1H), 2.02 (s, 3H), 2.07 (m, 1H), 2.15-2.30(m, 5H), 2.42 (d, 1H), 2.51 (s, 3H), 3.07 (t, 1H), 3.14 (t, 1H), 7.34(dd, 1H), 7.40 (d, 1H), 7.51 (d, 1H) P13

δ ppm 0.8-1.0 (m, 4H), 1.59 (m, 1H), 1.73 (m, 1H), 1.82 (m, 1H), 2.07(m, 1H), 2.15-2.30 (m, 5H), 2.40 (d, 1H), 2.53 (s, 3H), 3.09 (t, 1H),3.14 (t, 1H), 7.34 (dd, 1H), 7.40 (d, 1H), 7.51 (d, 1H) P14

δ ppm 1.05 (s, 9H), 1.74 (m, 1H), 1.84 (m, 1H), 2.08 (m, 1H), 2.15-2.30(m, 5H), 2.44 (d, 1H), 2.51 (s, 3H), 3.03 (t, 1H), 3.14 (t, 1H), 7.34(dd, 1H), 7.40 (d, 1H), 7.52 (d, 1H) P15

δ ppm 1.30 (t, 3H), 1.33 (s, 3H), 1.60 (m, 1H), 1.82 (m, 1H), 2.20 (m,1H), 2.24 (m, 2H), 2.40 (s, 3H), 2.45 (m, 1H), 2.9 (q, 2H), 3.05 (m,1H), 3.14 (m, 1H), 7.20 (m, 2H), 7.70 (m, 2H) P16

δ ppm 1.30 (t, 3H), 1.33 (s, 3H) 1.60 (m, 1H), 1.82 (m, 1H), 2.20 (m,1H), 2.24 (m, 2H), 2.45 (m, 1H), 2.90 (q, 2H), 3.05 (m, 1H), 3.14 (m,1H), 7.40 (m, 2H), 7.80 (m, 2H), 8.3 (s, 1H) P17

δ ppm 1.03 (s, 9H), 1.57 (m, 1H), 1.74 (m, 1H), 1.84 (m, 1H), 2.08 (m,1H), 2.21-2.31 (m, 1H), 2.45 (m, 1H), 3.02 (m, 1H), 3.16 (m, 1H), 6.54(t, 1H), 7.07 (dd, 1H), 7.23 (d, 1H), 8.18 (d, 1H) P18

δ ppm 1.75-1.96 (m, 5H), 2.05-2.56 (m, 7H), 3.15 (m, 2H), 7.42 (d, 2H),8.33 (d, 2H), 8.58 (s, 1H) P19

δ ppm 1.56 (s, 3H), 1.62 (s, 3H), 1.98 (s, 3H), 2.17-2.30 (m, 4H), 2.84(dt, 2H), 3.04 (m, 1H), 7.42 (d, 2H), 8.33 (d, 2H), 8.58 (s, 1H) P20

δ ppm 1.57 (s, 3H), 1.62 (m, 1H), 1.77 (m, 1H), 1.87 (m, 1H), 2.46 (s,3H), 2.66 (s, 3H), 2.98 (m, 2H), 8.40 (s, 1H) P21

δ ppm 0.88 (t, 3H), 1.25 (m, 4H), 1.52- 1.63 (m, 5H), 1.17 (m, 1H), 1.79(m, 1H), 2.03-2.23 (m, 3H), 2.36 (m, 2H), 2.45 (s, 3H), 2.51 (s, 3H),3.03 (m, 1H), 3.14 (m, 1H), 6.81 (s, 1H) P22

δ ppm 1.10 (s, 9H), 1.72 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 3.05 (m,2H), 7.40 (d, 2H), 7.80 (d, 2H), 8.4 (s, 1H) P23

δ ppm 1.10 (s, 9H), 1.72 (m, 1H), 1.85 (m, 2H), 2.15 (m, 3H), 2.30 (s,3H), 3.05 (m, 1H), 3.15 (m, 1H), 7.90 (d, 2H), 8.0 (d, 2H), 10.0 (s, 1H)P24

δ ppm 1.10 (s, 9H), 1.72 (m, 1H), 1.85 (m, 2H), 2.00 (m, 2H), 2.15 (m,3H), 2.30 (s, 3H), 3.05 (m, 2H), 7.40 (d, 2H), 7.80 (d, 2H)

Specific examples of the compounds of the invention include thosecompounds detailed in Tables 1 to 204.

Table 1:

This table covers 180 compounds of the structural type T-1:

wherein X is S, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined below:

Compound Number R³ R⁴ 1.001 CH₃ H 1.002 CH₃ CH₃ 1.003 CH₃ CH₃CH₂ 1.004CH₃ (CH₃)₂CH 1.005 CH₃ (CH₃)₃C 1.006 CH₃CH₂ H 1.007 CH₃CH₂ CH₃ 1.008CH₃CH₂ CH₃CH₂ 1.009 CH₃CH₂ (CH₃)₂CH 1.010 CH₃CH₂ (CH₃)₃C 1.011 CH₃Phenyl 1.012 CH₃ 2-fluorophenyl 1.013 CH₃ 3-fluorophenyl 1.014 CH₃4-fluorophenyl 1.015 CH₃ 2-chlorophenyl 1.016 CH₃ 3-chlorophenyl 1.017CH₃ 4-chlorophenyl 1.018 CH₃ 2-bromophenyl 1.019 CH₃ 3-bromophenyl 1.020CH₃ 4-bromophenyl 1.021 CH₃ 2-iodophenyl 1.022 CH₃ 3-iodophenyl 1.023CH₃ 4-iodophenyl 1.024 CH₃ 2-methylphenyl 1.025 CH₃ 3-methylphenyl 1.026CH₃ 4-methylphenyl 1.027 CH₃ 2-cyanophenyl 1.028 CH₃ 3-cyanophenyl 1.029CH₃ 4-cyanophenyl 1.030 CH₃ 2-methoxyphenyl 1.031 CH₃ 3-methoxyphenyl1.032 CH₃ 4-methoxyphenyl 1.033 CH₃ 2-trifluoromethylphenyl 1.034 CH₃3-trifluoromethylphenyl 1.035 CH₃ 4-trifluoromethylphenyl 1.036 CH₃4-trifluoromethoxyphenyl 1.037 CH₃ 4-difluoromethoxyphenyl 1.038 CH₃4-methylthiophenyl 1.039 CH₃ 4-methylsulfinylphenyl 1.040 CH₃4-methylsulfonylphenyl 1.041 CH₃ 4-trifluoromethylthiophenyl 1.042 CH₃4-trifluoromethylsulfinylphenyl 1.043 CH₃4-trifluoromethylsulfonylphenyl 1.044 CH₃ 2,3-difluorophenyl 1.045 CH₃2,4-difluorophenyl 1.046 CH₃ 2,5-difluorophenyl 1.047 CH₃2,6-difluorophenyl 1.048 CH₃ 3,4-difluorophenyl 1.049 CH₃3,5-difluorophenyl 1.050 CH₃ 2,3-dichlorophenyl 1.051 CH₃2,4-dichlorophenyl 1.052 CH₃ 2,5-dichlorophenyl 1.053 CH₃2,6-dichlorophenyl 1.054 CH₃ 3,4-dichlorophenyl 1.055 CH₃3,5-dichlorophenyl 1.056 CH₃ 4-bromo-2-fluorophenyl 1.057 CH₃4-bromo-3-fluorophenyl 1.058 CH₃ 4-bromo-2-chlorophenyl 1.059 CH₃4-bromo-3-chlorophenyl 1.060 CH₃ 4-chloro-2-cyanophenyl 1.061 CH₃4-chloro-3-cyanophenyl 1.062 CH₃ 4-chloro-2-fluorophenyl 1.063 CH₃4-chloro-3-fluorophenyl 1.064 CH₃ 4-chloro-2-methoxyphenyl 1.065 CH₃4-chloro-3-methoxyphenyl 1.066 CH₃ 4-chloro-2-methylphenyl 1.067 CH₃4-chloro-3-methylphenyl 1.068 CH₃ 4-chloro-2-trifluoromethylphenyl 1.069CH₃ 4-chloro-3-trifluoromethylphenyl 1.070 CH₃ 2-chloro-4-methoxyphenyl1.071 CH₃ 3-chloro-4-methoxyphenyl 1.072 CH₃ 2-chloro-4-methylphenyl1.073 CH₃ 3-chloro-4-methylphenyl 1.074 CH₃ 2-fluoro-4-methoxyphenyl1.075 CH₃ 3-fluoro-4-methoxyphenyl 1.076 CH₃ 2-fluoro-4-methylphenyl1.077 CH₃ 2-fluoro-4-methylphenyl 1.078 CH₃2-fluoro-4-trifluoromethylphenyl 1.079 CH₃3-fluoro-4-trifluoromethylphenyl 1.080 CH₃ 2-chloropyridin-5-yl 1.081CH₃ 3-chloropyridinyl-5-yl 1.082 CH₃ 2-methoxypyridin-5-yl 1.083 CH₃3-methoxypyridinyl-5-yl 1.084 CH₃ 2-methylpyridin-5-yl 1.085 CH₃3-methylpyridinyl-5-yl 1.086 CH₃ 2-trifluoromethylpyridin-5-yl 1.087 CH₃3-trifluoromethylpyridin-5-yl 1.088 CH₃ 2,6-dichloropyridin-3-yl 1.089CH₃ 4-chloropyrazol-1-yl 1.090 CH₃ 2-thiophenyl 1.091 CH₃5-chlorothiophen-2-yl 1.092 CH₃ 5-bromothiophen-2-yl 1.093 CH₃3-thiophenyl 1.094 CH₃ 5-chlorothiophen-3-yl 1.095 CH₃5-bromothiophen-3-yl 1.096 CH₃CH₂ phenyl 1.097 CH₃CH₂ 2-fluorophenyl1.098 CH₃CH₂ 3-fluorophenyl 1.099 CH₃CH₂ 4-fluorophenyl 1.100 CH₃CH₂2-chlorophenyl 1.101 CH₃CH₂ 3-chlorophenyl 1.102 CH₃CH₂ 4-chlorophenyl1.103 CH₃CH₂ 2-bromophenyl 1.104 CH₃CH₂ 3-bromophenyl 1.105 CH₃CH₂4-bromophenyl 1.106 CH₃CH₂ 2-iodophenyl 1.107 CH₃CH₂ 3-iodophenyl 1.108CH₃CH₂ 4-iodophenyl 1.109 CH₃CH₂ 2-methylphenyl 1.110 CH₃CH₂3-methylphenyl 1.111 CH₃CH₂ 4-methylphenyl 1.112 CH₃CH₂ 2-cyanophenyl1.113 CH₃CH₂ 3-cyanophenyl 1.114 CH₃CH₂ 4-cyanophenyl 1.115 CH₃CH₂2-methoxyphenyl 1.116 CH₃CH₂ 3-methoxyphenyl 1.117 CH₃CH₂4-methoxyphenyl 1.118 CH₃CH₂ 2-trifluoromethylphenyl 1.119 CH₃CH₂3-trifluoromethylphenyl 1.120 CH₃CH₂ 4-trifluoromethylphenyl 1.121CH₃CH₂ 4-trifluoromethoxyphenyl 1.122 CH₃CH₂ 4-difluoromethoxyphenyl1.123 CH₃CH₂ 4-methylthiophenyl 1.124 CH₃CH₂ 4-methylsulfinylphenyl1.125 CH₃CH₂ 4-methylsulfonylphenyl 1.126 CH₃CH₂4-trifluoromethylthiophenyl 1.127 CH₃CH₂ 4-trifluoromethylsulfinylphenyl1.128 CH₃CH₂ 4-trifluoromethylsulfonylphenyl 1.129 CH₃CH₂2,3-difluorophenyl 1.130 CH₃CH₂ 2,4-difluorophenyl 1.131 CH₃CH₂2,5-difluorophenyl 1.132 CH₃CH₂ 2,6-difluorophenyl 1.133 CH₃CH₂3,4-difluorophenyl 1.134 CH₃CH₂ 3,5-difluorophenyl 1.135 CH₃CH₂2,3-dichlorophenyl 1.136 CH₃CH₂ 2,4-dichlorophenyl 1.137 CH₃CH₂2,5-dichlorophenyl 1.138 CH₃CH₂ 2,6-dichlorophenyl 1.139 CH₃CH₂3,4-dichlorophenyl 1.140 CH₃CH₂ 3,5-dichlorophenyl 1.141 CH₃CH₂4-bromo-2-fluorophenyl 1.142 CH₃CH₂ 4-bromo-3-fIuorophenyl 1.143 CH₃CH₂4-bromo-2-chlorophenyl 1.144 CH₃CH₂ 4-bromo-3-chlorophenyl 1.145 CH₃CH₂4-chloro-2-cyanophenyl 1.146 CH₃CH₂ 4-chloro-3-cyanophenyl 1.147 CH₃CH₂4-chloro-2-fluorophenyl 1.148 CH₃CH₂ 4-chloro-3-fluorophenyl 1.149CH₃CH₂ 4-chloro-2-methoxyphenyl 1.150 CH₃CH₂ 4-chloro-3-methoxyphenyl1.151 CH₃CH₂ 4-chloro-2-methylphenyl 1.152 CH₃CH₂4-chloro-3-methylphenyl 1.153 CH₃CH₂ 4-chloro-2-trifluoromethylphenyl1.154 CH₃CH₂ 4-chloro-3-trifluoromethylphenyl 1.155 CH₃CH₂2-chloro-4-methoxyphenyl 1.156 CH₃CH₂ 3-chloro-4-methoxyphenyl 1.157CH₃CH₂ 2-chloro-4-methylphenyl 1.158 CH₃CH₂ 3-chloro-4-methylphenyl1.159 CH₃CH₂ 2-fluoro-4-methoxyphenyl 1.160 CH₃CH₂3-fluoro-4-methoxyphenyl 1.161 CH₃CH₂ 2-fluoro-4-methylphenyl 1.162CH₃CH₂ 3-fluoro-4-methylphenyl 1.163 CH₃CH₂2-fluoro-4-trifluoromethylphenyl 1.164 CH₃CH₂3-fluoro-4-trifluoromethylphenyl 1.165 CH₃CH₂ 2-chloropyridin-5-yl 1.166CH₃CH₂ 3-chloropyridinyl-5-yl 1.167 CH₃CH₂ 2-methoxypyridin-5-yl 1.168CH₃CH₂ 3-methoxypyridinyl-5-yl 1.169 CH₃CH₂ 2-methylpyridin-5-yl 1.170CH₃CH₂ 3-methylpyridinyl-5-yl 1.171 CH₃CH₂ 2-trifluoromethylpyridin-5-yl1.172 CH₃CH₂ 3-trifluoromethylpyridin-5-yl 1.173 CH₃CH₂2,6-dichloropyridin-3-yl 1.174 CH₃CH₂ 4-chloropyrazol-1-yl 1.175 CH₃CH₂2-thiophenyl 1.176 CH₃CH₂ 5-chlorothiophen-2-yl 1.177 CH₃CH₂5-bromothiophen-2-yl 1.178 CH₃CH₂ 3-thiophenyl 1.179 CH₃CH₂5-chlorothiophen-3-yl 1.180 CH₃CH₂ 5-bromothiophen-3-ylTable 2:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 3:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 4:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 5:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 6:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 7:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 8:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 9:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 10:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 11:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 12:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 13:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 14:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 15:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 16:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 17:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is C—H, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table 1.

Table 18:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are hydrogen andR³ and R⁴ are as defined in Table 1.

Table 19:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 20:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 21:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 22:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 23:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 24:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 25:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 26:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 27:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 28:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 29:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 30:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 31:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 32:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 33:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 34:

This table covers 180 compounds of the structural type T-1, wherein X isS, Z is N, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 35:

This table covers 180 compounds of the structural type T-2:

wherein X is S, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table 1.Table 36:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 37:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 38:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 39:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 40:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 41:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 42:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 43:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 44:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 45:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 46:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 47:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 48:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 49:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 50:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 51:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is C—H, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table 1.

Table 52:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are hydrogen andR³ and R⁴ are as defined in Table 1.

Table 53:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 54:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 55:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 56:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 57:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 58:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 59:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 60:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 61:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 62:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 63:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 64:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 65:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 66:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 67:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 68:

This table covers 180 compounds of the structural type T-2, wherein X isS, Z is N, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 69:

This table covers 180 compounds of the structural type T-1:

wherein X is Se, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table T1.Table 70:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 71:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 72:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 73:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 74:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 75:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 76:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 77:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 78:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 79:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen,R² is methyl and R³ and R⁴ are as defined in Table 1.

Table 80:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 81:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 82:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 83:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 84:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 85:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is C—H, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table 1.

Table 86:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 87:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 88:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 89:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 90:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 91:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 92:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 93:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 94:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 95:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 96:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 97:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 98:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 99:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 100:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 101:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 102:

This table covers 180 compounds of the structural type T-1, wherein X isSe, Z is N, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 103:

This table covers 180 compounds of the structural type T-2:

wherein X is Se, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table 1.Table 104:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 105:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 106:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 107:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 108:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 109:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 110:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 111:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 112:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 113:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen,R² is methyl and R³ and R⁴ are as defined in Table 1.

Table 114:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 115:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 116:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 117:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 118:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 119:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is C—H, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table 1.

Table 120:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 121:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 122:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 123:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 124:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 125:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 126:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 127:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 128:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 129:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 130:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 131:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 132:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 133:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 134:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 135:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 136:

This table covers 180 compounds of the structural type T-2, wherein X isSe, Z is N, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 137:

This table covers 180 compounds of the structural type T-1:

wherein X is O, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table T1.Table 138:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 139:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 140:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 141:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 142:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 143:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 144:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 145:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 146:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 147:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 148:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 149:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 150:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 151:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 152:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 153:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is C—H, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table 1.

Table 154:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are hydrogen andR³ and R⁴ are as defined in Table 1.

Table 155:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 156:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 157:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 158:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 159:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 160:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 161:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 162:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 163:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 164:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 165:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 166:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 167:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 168:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, Fe is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 169:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 170:

This table covers 180 compounds of the structural type T-1, wherein X isO, Z is N, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 171:

This table covers 180 compounds of the structural type T-2:

wherein X is O, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table 1.Table 172:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 173:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 174:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 175:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 176:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 177:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 178:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 179:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 180:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 181:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 182:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 183:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² aremethyl and R³ and R⁴ are as defined in Table 1.

Table 184:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 185:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl,R² is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 186:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 187:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is C—H, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R²are hydrogen and R³ and R⁴ are as defined in Table 1.

Table 188:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are hydrogen andR³ and R⁴ are as defined in Table 1.

Table 189:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is CH(CH₃), G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 190:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is C(CH₃)₂, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 191:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 192:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is CH₂, G is hydrogen, R¹ and R² are methyl andR³ and R⁴ are as defined in Table 1.

Table 193:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are hydrogenand R³ and R⁴ are as defined in Table 1.

Table 194:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 195:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 196:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 197:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ is hydrogen, R² ismethyl and R³ and R⁴ are as defined in Table 1.

Table 198:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is hydrogen, R²is methyl and R³ and R⁴ are as defined in Table 1.

Table 199:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is —CH═CH—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 200:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is CH₂, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² are methyland R³ and R⁴ are as defined in Table 1.

Table 201:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is C(CH₃)₂, E is —CH═CH—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 202:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is C(CH₃)₂, E is —CH₂—CH₂—, G is hydrogen, R¹ is methyl, R²is hydrogen and R³ and R⁴ are as defined in Table 1.

Table 203:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is —CH₂CH₂—, E is —CH═CH—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

Table 204:

This table covers 180 compounds of the structural type T-2, wherein X isO, Z is N, D is —CH₂—CH₂—, E is —CH₂—CH₂—, G is hydrogen, R¹ and R² arehydrogen and R³ and R⁴ are as defined in Table 1.

BIOLOGICAL EXAMPLES Example A

Seeds of a variety of test species were sown in standard soil in pots.After cultivation for one day (pre-emergence) or after 10 dayscultivation (post-emergence) under controlled conditions in aglasshouse, the plants were sprayed with an aqueous spray solutionderived from the formulation of the technical active ingredient in 0.6ml acetone and 45 ml formulation solution containing 10.6% Emulsogen EL(Registry number 61791-12-6), 42.2% N-methylpyrrolidone, 42.2%dipropylene glycol monomethyl ether (Registry number 34590-94-8) and0.2% X-77 (Registry number 11097-66-8). The test plants were then grownin a greenhouse under optimum conditions until, 14 or 15 days later forpost-emergence and 19 or 20 days for pre-emergence, the test wasevaluated (100=total damage to plant; 0=no damage to plant).

Test Plants:

Alopecurus myosuroides (ALOMY), Avena fatua (AVEFA), Lolium perenne(LOLPE), Setaria faberi (SETFA), Digitaria sanguinalis (DIGSA),Echinochloa crus-galli (ECHCG)

Pre-Emergence Activity

Com- pound Rate Number g/ha ALOMY AVEFA LOLPE SETFA DIGSA ECHCG T1 25060 20 80 70 60 60 T15 250 90 — 100 100 100 100 T16 250 10 20 20 80 80 70T17 250 100 100 100 100 100 100 T18 250 0 0 0 20 30 20 T19 250 100 100100 100 100 100 T23 250 30 50 0 0 0 0Post-Emergence Activity

Com- pound Rate Number g/ha ALOMY AVEFA LOLPE SETFA DIGSA ECHCG T1 12570 70 30 90 80 100 T15 125 90 90 50 100 100 70 T16 125 20 40 20 60 70 50T17 125 70 50 40 80 80 90 T18 125 40 30 20 60 60 50 T19 125 100 100 80100 100 100 T23 125 80 70 70 100 90 90

Example B

Seeds of a variety of test species were sown in standard soil in pots.After cultivation for one day (pre-emergence) or after 8 dayscultivation (post-emergence) under controlled conditions in a glasshouse(at 24/16° C., day/night; 14 hours light; 65% humidity), the plants weresprayed with an aqueous spray solution derived from the formulation ofthe technical active ingredient in acetone/water (50:50) solutioncontaining 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN9005-64-5).

The test plants were then grown in a glasshouse under controlledconditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65%humidity) and watered twice daily. After 13 days for pre andpost-emergence, the test was evaluated (100=total damage to plant; 0=nodamage to plant).

Test Plants:

Alopecurus myosuroides (ALOMY), Avena fatua (AVEFA), Setaria faberi(SETFA), Echinochloa crus-galli (ECHCG), Solanum nigrum (SOLNI) andAmaranthus retoflexus (AMARE)

Pre-Emergence Activity

Com- pound Rate Number g/ha AMARE SETFA ALOMY ECHCG AVEFA T2 250 0 50 00 0 T3 250 0 90 60 80 0 T4 250 0 30 50 60 0 T5 250 0 90 50 80 0 T9 250 050 30 50 0 T10 250 0 20 20 60 0 T11 250 0 0 40 70 0 T13 250 0 100 90 10040 T14 1000 0 70 30 90 80 T20 250 0 40 50 70 0 T22 250 20 100 70 80 20T26 250 0 100 90 100 60 T27 250 0 100 90 100 90 T28 250 0 100 80 100 90T29 250 20 100 90 100 90 T30 250 20 100 90 100 100 T32 250 0 100 90 10080 T33 250 0 100 90 100 50 T34 250 0 20 20 20 0 T35 250 0 100 30 90 0T36 250 0 70 60 60 20 T37 250 0 90 30 60 30 T38 250 0 100 60 70 50 T39250 0 90 90 100 0 T40 250 0 100 100 100 100 T41 250 0 40 80 100 0 T42250 0 100 100 100 0 T44 250 0 100 90 100 60 T45 250 0 100 90 100 30 T46250 0 90 60 100 30 T49 250 0 100 100 100 100 T51 250 0 100 80 100 20 T53250 0 100 90 100 80 T54 250 0 60 90 100 70 T55 250 0 100 100 100 100 T56250 0 0 0 40 0 T57 250 0 90 60 90 20 T58 250 0 60 60 100 60 T59 250 0100 80 90 70 T63 250 0 90 90 100 90 T64 250 0 0 20 0 0 T65 250 20 100 50100 20 T66 250 0 30 10 30 0 T68 250 0 80 60 0 70 T70 250 100 100 70 6030 T73 250 0 0 0 0 50 T74 250 100 40 30 20 0 T75 250 0 90 0 40 20 T76250 0 70 0 50 0 T77 250 50 0 0 0 0 T78 250 0 0 0 0 90 T81 250 0 100 50100 40 T82 250 0 80 0 40 0 T83 250 0 90 50 100 0 T84 250 0 100 70 100 40T85 250 30 0 0 0 0 T87 250 20 60 20 60 50 T88 250 0 80 0 60 0 T92 250 0100 70 100 90 T93 250 0 20 20 40 0 T96 250 0 100 80 100 100 T99 250 2060 50 60 30 T102 250 0 50 50 70 30 T104 250 0 50 70 100 20 T106 250 0 200 10 0 T110 250 20 100 30 60 30 T111 250 0 80 50 100 90 P1 250 0 100 80100 0 P2 250 0 100 80 100 40 P3 250 0 100 20 80 0 P4 250 40 90 0 0 0 P5250 0 100 100 40 30 P6 250 0 100 20 20 0 P7 250 0 90 30 20 0 P8 250 0100 20 50 0 P9 250 0 100 90 90 100 P11 250 0 80 0 0 0 P12 250 0 100 3020 20 P13 250 0 100 70 50 100 P14 250 0 100 70 100 100 P15 250 0 90 90100 60 P17 250 0 100 80 100 50 P18 250 0 60 20 70 0 P19 250 0 90 10 20 0P22 250 0 30 0 0 0Post-Emergence Activity

Com- pound Rate Number g/ha AMARE SETFA ALOMY ECHCG AVEFA T2 250 0 70 030 0 T3 250 0 100 90 100 60 T4 250 0 80 60 100 T5 250 0 100 70 100 0 T6250 0 50 0 40 0 T9 250 0 100 60 70 0 T10 250 0 70 20 70 0 T11 250 0 8090 100 40 T13 250 0 100 100 100 90 T14 1000 20 100 90 100 90 T20 250 090 90 100 90 T22 250 0 90 90 90 90 T24 250 0 30 0 0 0 T25 1000 0 30 2010 0 T26 250 40 100 100 100 100 T27 250 0 100 100 100 100 T28 250 0 100100 100 100 T29 250 0 100 100 100 100 T30 250 0 100 100 100 100 T31 2500 80 0 60 0 T32 250 0 100 100 100 90 T33 250 0 100 100 100 100 T34 250 090 70 80 0 T35 250 0 100 100 100 80 T36 250 0 100 90 100 20 T37 250 0100 100 100 90 T38 250 0 100 100 100 100 T39 250 0 100 100 100 100 T40250 0 100 100 100 100 T41 250 0 100 100 100 70 T42 250 0 100 100 100 70T43 250 0 60 20 20 0 T44 250 0 100 100 100 100 T45 250 0 100 100 100 100T46 250 0 100 100 100 90 T47 250 0 90 30 80 0 T48 250 0 80 20 80 0 T49250 0 100 90 100 90 T51 250 0 100 100 100 100 T52 250 0 0 0 0 0 T53 2500 100 100 100 100 T54 250 30 100 100 100 90 T55 250 0 100 100 100 100T56 250 0 70 0 60 0 T57 250 0 100 70 100 60 T58 250 0 100 90 100 80 T59250 0 100 100 100 80 T60 250 0 60 0 50 0 T61 250 0 20 0 0 0 T62 250 0 600 0 0 T63 250 0 100 60 100 70 T64 250 0 70 0 50 0 T65 250 70 100 50 10070 T66 250 0 70 10 70 0 T68 250 0 100 70 100 90 T70 250 40 100 90 100 50T71 250 0 50 0 20 0 T73 250 0 30 0 20 0 T74 250 0 90 50 70 0 T75 250 090 20 70 0 T76 250 0 80 70 90 50 T77 250 0 70 0 60 0 T78 250 0 80 60 700 T79 250 0 10 0 0 0 T81 250 0 100 50 100 50 T82 250 30 100 20 100 0 T83250 0 100 60 100 100 T84 250 40 100 90 100 70 T87 250 0 90 50 90 60 T88250 0 70 10 90 0 T89 250 0 80 0 30 0 T90 250 0 40 0 30 0 T92 250 10 100100 100 100 T93 250 0 70 30 70 0 T95 250 0 80 80 70 30 T96 250 30 100100 100 100 T97 250 0 70 0 70 0 T98 250 0 70 20 70 0 T99 250 0 100 100100 100 T102 250 0 100 100 100 100 T104 250 0 100 100 100 90 T106 250 070 10 30 0 T107 250 0 0 0 60 0 T110 250 0 100 60 90 70 T111 250 0 100100 100 100 T112 250 0 100 70 100 80 T113 250 0 90 90 100 100 T114 250 090 10 60 0 T118 250 0 80 60 60 80 T120 250 0 90 40 100 60 T121 250 0 9070 100 80 P1 250 0 100 100 100 100 P2 250 0 100 100 100 100 P3 250 0 10060 80 0 P4 250 0 80 20 80 0 P5 250 0 100 100 100 90 P6 250 0 100 90 10080 P7 250 0 100 90 100 90 P8 250 0 100 70 0 80 P9 250 0 100 100 100 100P11 250 0 80 20 80 20 P12 250 0 100 100 100 90 P13 250 0 100 90 100 90P14 250 0 100 100 100 90 P15 250 0 100 100 100 90 P17 250 0 100 90 10080 P18 250 40 90 10 80 0 P19 250 0 90 20 90 0 P22 250 0 70 0 20 0 P23250 0 30 0 20 0

What is claimed is:
 1. A compound of formula I

wherein R¹ and R² are independently of each other hydrogen, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆haloalkenyloxy, C₃-C₆alkynyloxy,C₁-C₄alkoxyC₁-C₄alkyl, C₁-C₄alkoxyC₁-C₄alkoxy,C₁-C₄alkoxyC₁-C₄alkoxyC₁-C₄alkyl, C₁-C₆alkylthio,C₁-C₄alkylthioC₁-C₄alkyl, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfinylC₁-C₄alkyl, C₁-C₄alkylsulfonyl,C₁-C₄alkylsulfonylC₁-C₄alkyl, hydroxy-C₁-C₄alkyl,C₁-C₆haloalkoxyC₁-C₄alkyl, C₃-C₆alkenyloxyC₁-C₄alkyl,C₃-C₆haloalkenyloxyC₁-C₄alkyl, C₃-C₆alkynyloxyC₁-C₄alkyl,C₁-C₆cyanoalkyl, C₁-C₆cyanoalkoxy, C₁-C₄cyanoalkoxyC₁-C₄alkyl, hydroxy,C₁-C₆alkylcarbonyl, carboxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkylaminocarbonyl, di-C₁-C₆alkylaminocarbonyl,tri(C₁-C₄alkyl)silyl or tri(C₁-C₄alkyl)silyloxy, D is optionallysubstituted C₁-C₃alkylene, E is optionally substituted C₁-C₃alkylene oroptionally substituted C₂-C₃alkenylene, Het is a an optionallysubstituted monocyclic or bicyclic heteroaromatic ring; and G ishydrogen, an alkali metal, alkaline earth metal, sulfonium, ammonium ora latentiating group.
 2. The compound according to claim 1, wherein R¹is hydrogen, C₁-C₄ alkyl or C₁-C₄alkoxy.
 3. The compound according toclaim 1, wherein R² is hydrogen or methyl.
 4. The compound according toclaim 1, wherein D is C₁-C₂alkylene or C₁-C₂alkylene substituted byC₁-C₃ alkyl or C₁-C₃alkoxyC₁-C₃alkyl.
 5. The compound according to claim1, wherein E is optionally substituted C₁-C₂alkylene or optionallysubstituted C₂alkenylene.
 6. The compound according to claim 1, whereinHet is an optionally substituted monocyclic 5- or 6-membered nitrogen orsulfur containing heteroaromatic ring.
 7. The compound according toclaim 6, wherein Het is a group of the formula R₁ to R₁₂

wherein A designates the point of attachment to the ketoenol moiety, W¹is N or CR⁶, W² and W³ are independently of each other N or CR⁴, W⁴ is Nor CR⁷, with the proviso that at least one of W¹, W², W³ or W⁴ is N, Xis O, S, Se, or NR⁹, Z is N or CR¹⁰ , wherein R³ is hydrogen, halogen,C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆-halocycloalkyl,C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,nitro or cyano, R⁴ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₅-C₆cycloalkenyl, halogen, C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆haloalkoxy, optionally substituted aryl, optionally substitutedaryloxy, optionally substituted heteroaryl or optionally substitutedheteroaryloxy, R⁵ is hydrogen, C₁-C₄ alkyl, C₂-C₃alkenyl, C₂-C₃alkynyl,C₁-C₄ haloalkyl or C₂-C₃ haloalkenyl, R⁶ is hydrogen, methyl, halomethylor halogen R⁷ is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄alkenyl, C₂-C₄ haloalkenyl, C₂-C₄ alkynyl, C₁-C₄ alkoxy, C₁-C₄haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl orcyano, R⁸ is hydrogen, methyl, ethyl, halomethyl, haloethyl, optionallysubstituted aryl or optionally substituted heteroaryl, R⁹ is hydrogen,methyl, ethyl or halomethyl, and R¹⁰ is hydrogen, methyl, ethyl,halomethyl, haloethyl, halogen, cyano or nitro.
 8. The compoundaccording to claim 7, wherein Het is a group of the formula R₂

wherein X is sulphur, Z is nitrogen or CR¹⁰ and R³, R⁴ and R¹⁰ have themeanings assigned to them in claim
 7. 9. A process for the preparationof a compound of formula (G), which is a compound of the formula I asdefined in claim 1, wherein G is hydrogen, Het is a group of the formulaR₂

wherein A designates the point of attachment to the ketoenol moiety offormula I, X is O, S, Se, or NR⁹, Z is N or CR¹⁰, R⁹ is hydrogen,methyl, ethyl or halomethyl, R¹⁰ is hydrogen, methyl, ethyl, halomethyl,haloethyl, halogen, cyano or nitro, R¹, R², E and D have the meaningassigned to them in claim 1, R³ is CH₂R″, R″ is hydrogen, alkyl orhalogenoalkyl, and R⁴ is hydrogen, C₁-C₆alkyl, C₁-C₆ haloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₃-C₆ cycloalkyl,C₅-C₆cycloalkenyl, halogen, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆haloalkoxy,optionally substituted aryl, optionally substituted aryloxy, optionallysubstituted heteroaryl or optionally substituted heteroaryloxy, whichcomprises the thermal rearrangement optionally in the presence of asuitable solvent and optionally under microwave irradiation of thecompound of the formula (H) into a compound of formula (G)


10. A process for the preparation of a compound of formula (J), which isa compound of the formula I as defined in claim 1, wherein G ishydrogen, Het is a group of the formula R₃

wherein A designates the point of attachment to the ketoenol moiety offormula I, X is O, S, Se, or NR⁹, Z is N or CR¹⁰, R⁹ is hydrogen,methyl, ethyl or halomethyl, R¹⁰ is hydrogen, methyl, ethyl, halomethyl,haloethyl, halogen, cyano or nitro, R¹, R², E and D have the meaningassigned to them in claim 1, R³ is CH₂R″, R″ is hydrogen, alkyl orhalogenoalkyl, and R⁴ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₃-C₆ cycloalkyl,C₅-C₆cycloalkenyl, halogen, C₁-C₆alkoxy, C₁-C₆alkoxy-C₁C₆alkyl,C₁-C₆haloalkoxy, optionall substituted aryl, optionally substitutedaryloxy, optionally substituted heteroaryl or optionally substitutedheteroaryloxy, which comprises the thermal rearrangement optionally inthe presence of a suitable solvent and optionally under microwaveirradiation of the compound of the formula (K) into a compound offormula (J)


11. A method of controlling grasses and weeds in crops of useful plants,which comprises applying a herbicidally effective amount of a compoundof formula I, as defined in claim 1, or of a composition comprising sucha compound, to the plants or to the locus thereof.
 12. A herbicidalcomposition comprising: a compound of formula I according to claim 1;and a formulation adjuvant.
 13. The composition according to claim 12,which, in addition to comprising the compound of formula I, comprises afurther herbicide as mixing partner.
 14. The composition according toclaim 12, which, in addition to comprising the compound of formula I,comprises a safener.
 15. The composition according to claim 12, which,in addition to comprising the compound of formula I, comprises a furtherherbicide as mixing partner and a safener.